text:
▷ So-Yeon Kim, Jeongmook Lee, and Sang Kyu Kim, Young S. Choi
"Nonplanar structure of C6H5SCF3 facilitates πσ*-mediated
photodissociation reaction on the S1 state"
Chemical Physics Letters, 659, 43-47 (2016)
Vibrational structure of trifluoromethylthiobenzene (C6H5SCF3) on the S1 state has been investigated by resonance-enhanced two-photon ionization spectroscopy and nature of predissociation dynamics is inferred from homogeneously broadened spectral features. As (C6H5SCF3) adopts a nonplanar structure in both the S0 and S1 states, the effective adiabatic barrier generated by avoided crossing of opticallybright bound S1 (ππ*) and dark-repulsive S2 (πσ*) surfaces along the reaction coordinate is significantly lowered, giving the S1 lifetime of ~300 fs. This experiment demonstrates that the molecular structure spanned by the reactive flux near the curve-crossing region dictates reaction rate as well as nonadiabatic transition probability.
▷ So-Yeon Kim, Jeongmook Lee, and Sang Kyu Kim
"H/D Substitution Makes Difference in Photochemical Studies:
the Case of Dimethylamine"
Rapid Communication in Photoscience, 4, 3, 63-66 (2015)
When the molecule in the excited state is subject to prompt predissociation, it is quite nontrivial to obtain vibrational structure of the excited state in general. This applies to the case of photochemistry of dimethylamine (DMA:(CH3)2NH). When DMA is excited to its first electronically excited state (S1), the N-H bond dissociation occurs promptly. Therefore, S1 vibronic bands are homogeneously broadened to give extremely small ionization cross sections and heavily-congested spectral features, making infeasible any reasonable spectral assignment. Here, we demonstrate that the predissociation rate of the excited state could be significantly reduced by the NH/ND substitution to give the much better-resolved S1 spectral feature, revealing the vibrational structure of the excited state of DMA-d1 ((CH3)2ND) for the first time.
▷ Hyun Sik You, Songhee Han, Jun-Ho Yoon, Jeong Sik Lim, Jeongmook Lee,
So-Yeon Kim, Doo-Sik Ahn, Jean Sun Lim, and Sang Kyu Kim
"Structure and Dynamic Role of Conical Intersections
in the πσ*-mediated Photodissociation Reactions"
International Reviews in Physical Chemistry, 34, 3, 429-459 (2015)
Conical intersection as a dynamic funnel in nonadiabatic transition dictates many important chemical reaction outputs such as reaction rates, yields, and energy disposals especially for chemical reactions taking place on electronically excited states. Therefore, the energetics and topology of conical intersections have been subjected to intensive theoretical and experimental studies for decades as these things are the keys to understanding and controlling nonadiabatic transitions which are ubiquitous in nature. In this article, we focus on πσ*-mediated photodissociation reactions of thiophenols and thioanisoles. Interestingly, for these chemical systems, the nonadiabatic transition probability can be precisely measured as a function of the excitation energy, giving a great opportunity for spectroscopic characterization of the multi-dimensional conical intersection seam that governs the nonadiabatic transition dynamics of polyatomic molecules. The passage of the reactive flux in the proximity of the conical intersection gives rise to dynamic resonances corresponding to dramatic state-specific increases of the nonadiabatic transition probability. Accordingly, it is found that the electronic and nuclear configurations of the reactive flux and their evolution, coupled to the conical intersection seam, are critical in nonadiabatic transition dynamics. Nonadiabaticity is found to be extremely sensitive to the conformational molecular structure, and this has been demonstrated in the photodissociation dynamics of the chemical derivatives of thiophenol. Intramolecular vibrational redistribution, which is nontrivial in surmounting the reaction barrier, is found to wash out state-specific dynamic resonances, implying the importance of the dynamic interplay between vibrational energy flow and nonadiabatic transition. The experimental results on conical intersection dynamics presented in this review provide many interesting and important issues to be pursued in the near future by both theoreticians and experimentalists.
▷ Hyun Sik You, Songhee Han, Jean Sun Lim, and Sang Kyu Kim
"(ππ*/πσ*) Conical Intersection Seam Experimentally Observed in the S–D Bond Dissociation Reaction of Thiophenol-d1"
J. Phys. Chem. Lett., 6, 3202-3208 (2015)
Surface crossing of bound (S1, ππ*) and continuum (S2, πσ*) states has been observed in the ultrafast S–D bond dissociation reaction of thiophenol-d1. It is manifested by an unanticipated variation of fragment angular distribution as a function of the excitation energy. The anisotropy parameter (β) of +0.25 at the S1 origin decreases to -0.60 at ∼600 cm–1 above the S1 zero-point level, giving a broad peak in β with a bandwidth of ∼200 cm–1. The peak in β is ascribed to the in-plane S-D bending mode excitation by which the nuclear configuration in the proximity of the S1/S2 conical intersection seam is directly accessed, showing a mixed character of parallel (S1–S0) and perpendicular (S2–S0) transition dipole moments at the same time. As a result, the dynamic aspect of the conical intersection is experimentally revealed here through direct access to the nuclear configuration on the multidimensional conical intersection seam.
▷ Songhee Han, Hyun Sik You, So-Yeon Kim, and Sang Kyu Kim
"Dynamic Role of the Intramolecular Hydrogen Bonding in Nonadiabatic Chemistry Revealed in the UV Photodissociation Reactions of 2-Fluorothiophenol and 2-Chlorothiophenol"
J. Phys. Chem. A, 118, 6940-6949 (2014)
The dynamic interplay between the intramolecular hydrogen bonding and intramolecular vibrational redistribution is found to be critical in nonadiabatic reaction dynamics. Herein, it has been demonstrated that the molecular planarity, directed by the intramolecular hydrogen bonding, plays an important role in the nonadiabatic passage of the reactive flux at the conical intersection in the photodissociation reactions of 2-fluorothiophenol and 2-chlorothiophenol. As the internal energy increases in the excited state, the intramolecular hydrogen bonding of 2-fluorothiophenol loosens. The floppiness brought into the molecular structure then modifies the dynamic path of the reactive flux, leading to the diminishment of the nonadiabatic transition probability at the conical intersection. On the contrary, for 2-chlorothiophenol having the relatively stronger intramolecular hydrogen bonding, the reactive flux seems to retain the molecular planarity even with the increase of the internal energy as manifested by the constant nonadiabatic transition probability over the wide range of the S1 internal energy. The effect of the intramolecular hydrogen bonding on the molecular structure and its relation to the nonadiabatic dynamics along the tunneling path has been experimentally demonstrated.
▷ Dahyi Jeong, Ki Young Yeon, and Sang Kyu Kim
"Tip-enhanced Electron Emission Microscopy Coupled with the Femtosecond Laser Pulse"
Bull. Korean Chem. Soc., 35, 891 (2014)
The ultrashort electron pulse, laser-emitted from the metal tip apex has been characterized and used as a probing source for a new electron microscope to visualize the morphology of the gold-mesh in the nanometric resolution. As the gap between the tungsten tip and Au-surface is approached within a few nm, the large electromagnetic field enhancement for the incident P-polarized laser pulse with respect to the tip-sample axis is strongly observed. Here, we demonstrate that the time-resolved tip-enhanced electron emission microscope (TEEM) can be implemented on the laboratory table top to give the two-dimensional image, opening lots of challenges and opportunities in the near future.
▷ Jun-Ho Yoon, Kyung Chul Woo, and Sang Kyu Kim
"Vibronic Structures and Dynamics of the Predissociating Dimethyl Sulfide and its Isotopomers (CH3SCH3, CD3SCD3, CH3SCD3) at the Conical Intersection"
Phys. Chem. Chem. Phys., 16, 8949-8955 (2014)
Conical intersection seam comprised of crossing surfaces of two lowest excited states of dimethyl sulfide (DMS) has been directly accessed by the one-photon excitation from the ground equilibrium state. Since the S-C bond rupture takes place promptly, the molecular structure on the excited state effectively belongs to CS symmetry. Namely, excited states of 11B1 and 11A2 in C2V become 11A′ and 21A′ states in CS, respectively, and the optical transition from the ground equilibrium state to the dissociating molecule at the conical intersection seam is symmetry-allowed to facilitate the nonadiabatic transition on the 21A′ state, leading eventually to the CH3S + CH3 products. The dynamic study of DMS, in this sense, gives the great opportunity to unravel the vibronic structure of the conical intersection seam by the conventional one-photon excitation method. In this work, utilizing the photofragment excitation (PHOFEX) spectroscopic method, the vibronic structures of DMS and its isotope analogs (CD3SCD3, CH3SCD3) at the conical intersection seam have been revealed, providing accurate lifetimes and detailed dynamics associated with individual vibronic transitions. Lifetime of the excited DMS is estimated to be ~ 100 fs, indicating that the dissociation is complete within one single oscillation in the conical intersection region. It is also found that the symmetric CSC stretching mode is strongly coupled to the reaction coordinate, as manifested by our experimental finding that the fragmentation yield of the S-CD3 bond is enhanced compared to that of the S-CH3 bond in the CH3SCD3 dissociation reaction only when the CSC symmetric stretching vibrational mode is excited at the conical intersection region. This work demonstrates that the better understanding of the excited state could make the bond-selective chemistry into reality.
▷ Jeongmook Lee, So-Yeon Kim, and Sang Kyu Kim
"Spectroscopic Separation of the Methyl Internal Rotational Isomers of Thioanisole Isotopomers (C6H5S-CH2D and C6H5S-CHD2)"
J. Phys. Chem. A, 118, 1850 (2014)
Two distinct rotational isomers of thioanisole-d1 (C6H5S-CH2D) and thioanisole-d2 (C6H5S-CHD2) with respect to the internal rotation of the methyl moiety have been identified and characterized spectroscopically using the resonantly-enhanced two photon ionization (R2PI), UV-UV hole burning, and slow-electron velocity map imaging (SEVI) techniques. From the statistical weights, the definite assignment for the specific rotational isomer of each isotopomer has been successfully done, providing isomer-specific ionization energies and vibrational frequencies of S1/D0 states. Detailed molecular structures, the methyl internal-rotor barrier, and normal mode descriptions for selective vibrations are discussed with the aid of density functional theory calculations.
▷ Songhee Han, Jeong Sik Lim, Jun-Ho Yoon, Jeongmook Lee, So-Yeon Kim, and Sang Kyu Kim
"Conical Intersection Seam and Bound Resonances Embedded in Continuum Observed in the Photodissociation of Thioanisole-d3"
J. Chem. Phys., 140, 054307 (2014)
Herein, the multi-dimensional nature of the conical intersection seam has been experimentally revealed in the photodissociation reaction of thioanisole-d3 (C6H5SCD3) excited on S1, giving C6H5S· ( or ) + ·CD3 products. The translational energy distribution of the nascent ·CD3 fragment, reflecting the relative yields of the C6H5S· () and C6H5S· () products, was measured at each S1 vibronic band using the velocity map ion imaging technique. Direct access of the reactant flux to the conical intersection seam leads to the increase of the nonadiabatic transition probability resulting in sharp resonances in the / C6H5S· product branching ratio at several distinct S1 vibronic bands. The nature of the S1 vibronic bands associated with such dynamic resonances was clarified by the mass-analyzed threshold ionization spectroscopy. The bound state embedded in continuum generated by the conical intersection is observed as a distinct dynamic resonance, revealing the nature of the nuclear motion responsible for the nonadiabatic coupling of two potential energy surfaces at the conical intersection. The multi-dimensional facets of the conical intersection seam in terms of its detailed structure and dynamic role are discussed with the aid of theoretical calculations.
"Spectroscopic Study on Nonradiative Transition and Ionization of
5-methylpyrimidine at S1 Probed by the Slow-electron Velocity-map Imaging (SEVI) Technique"
Phys. Lett., 568, 36 (2013)
Slow electron velocity-map
imaging (SEVI) has been employed for the ionization spectroscopic study of the jet-cooled 5-methylpyrimidine in the first singlet 1(nπ*) excited
state. Resonant-enhanced two-color two-photon (1+1') ionization spectrum gives
well-resolved S1 vibrational structures up to ~ 2400 cm-1
above the origin whereas spectral bands becomes completely broadened in the
higher energy region as coupling of individual S1 bands to dark
states becomes significant. Ionization of the S1 5-methylpyrimidine with
different ionization wavelengths at several different delay times reveals the
property of low-lying 3(ππ*) triplet dark state which is prepared by
fast nonadiabatic transition. SEVI spectra taken via various S1
intermediate states provide the detailed vibrational structures of the
5-methylpyrimidine cation (D0), also giving the adiabatic ionization
energy of 9.1052 ±
0.0030 eV (73 438 ±
24 cm-1). Geometrical changes in the S0-S1-D0
transitions are discussed from Franck-Condon simulations based on calculations by
(time-dependent) density functional theory.
▷ Jeongmook Lee, Doo-Sik Ahn, and Sang Kyu Kim
"Valence Electron Ionization Dynamics of Chromium by a Photoelectron Imaging Technique:
J+ -Dependent State and Angular
J. Phys. Chem. A, 117, 2138 (2013)
The photoionization of Cr at excited states is investigated using a velocity-map photoelectron imaging technique. Benzene chromium carbonyl or bis(η6- benzene) chromium was used as a precursor for the generation of excited Cr atoms. The a5S2 → x5P°3 and a5D3 → y5D°2 transitions are then employed for the preparation of
resonant intermediate states in a two-color two-photon ionization process, in which an electronic configurational
change from 3d4(5D)4s4p(1P°) to 3d44s(6DJ+) occurs. The photo- electron kinetic energy distribution is found to be very sensitive to the ionization energy and the total angular momentum quantum number of the chromium ion (J+). Anisotropy parameters associated with departing electrons also show significant variation depending on the energy and total angular momentum quantum number, suggesting that direct and/or indirect ionization
should be quantum-mechanically mixed, manifesting the complicated nature of
angular momentum couplings in the ionization continuum.
▷ Jun-Ho Yoon, Jeong Sik Lim, Kyung Chul Woo, Myung Soo Kim, and Sang Kyu Kim
"Chemical Substitution Effect on Energetic and Structural Differences between
Ground and First Electronically Excited States of Thiophenoxyl Radicals"
Bull. Korean Chem. Soc., 34, 415 (2013)
Effect of chemical substitution at the para-position of the thiophenoxyl radical has been theoretically investigated in terms of energetics, structures, charge densities and orbital shapes for the ground and first electronically excited states. It is found that the adiabatic energy gap increases when CH3 or F is substituted at
the para-position. This change is attributed to the stabilization of the ground state of thiophenoxyl radical through
the electron-donating effect of F or CH3 group as the charge or spin of the singly-occupied molecular orbital is delocalized over the entire molecule especially in the ground state whereas in the excited state it is rather localized on sulfur and little affected by chemical substitutions. Quantitative comparison of predictions based on four different quantum-mechanical calculation methods is presented.
▷ Doo-Sik Ahn, Jeongmook Lee, Young Choon Park, Yoon Sup Lee, and Sang Kyu Kim
"Nuclear motion Captured by the slow electron velocity imaging technique
in the tunnelling predissociation of the S1 methylamines"
J. Chem. Phys., 136, 024306 (2012)
Predissociation dynamics of methylamines (CH3NH2 and CH3ND2) on the first electronically excitedstates are studied using the slow-electron velocity imaging method to unravel the multi-dimensional nature of the N–H(D) chemical bond dissociation reaction which occurs via tunnelling.
nearly free internal rotation around the C–N bond axis is found to be strongly coupled to the reaction pathway,
revealing nuclear motions actively involved in the tunnelling process on the S1 potential energy surfaces. The vibrational state-resolved energy and angular distributions of photoelectron, ejected from the ionization mediated by the metastable intermediate S1 state provide a unique way for mapping the predissociative potential energy surfaces.
▷ Songhee Han, Hyun Sik Yoo, Doo-Sik Ahn, Young S. Choi, and Sang Kyu Kim
"Vacuum ultraviolet mass-analyzed threshold ionization spectroscopy of
methylcyclohexane in the supersonic jet"
Chem. Phys. Lett., 518, 38 (2011)
Vacuum ultraviolet (VUV) mass-analyzed threshold ionization (MATI) spectrum of supersonically cooled methylcyclohexane has been obtained to give the precise adiabatic ionization energy of 9.6958 ± 0.0025 eV for the chair equatorial conformer. Vibrationally resolved MATI spectrum has been analyzed with the aid
of density functional theory and Franck–Condon calculations. The MATI
spectrum reflects the structural change upon ionization and its origin is discussed by inspecting the shapes of the valence orbitals involved in the ionization process. The spectroscopic implication of the structural interconversion above the certain energy level is discussed with theoretical calculations of molecular structures and energetics.
▷ Kuk Ki Kim, Daehyun Kim, Sang Kyu Kim, Seung Min Park, Jae Kyu Song
"Formation of ZnO nanoparticles by laser ablation in neat water"
Chem. Phys. Lett., 511, 116-120 (2011)
Zinc oxide (ZnO) nanoparticles were prepared in neat deionized water by laser ablation with various ablation times (10 – 40 min), fluences (50 – 130
mJ/pulse), and wavelengths (1064, 532, and 355 nm). The size and shape of the nanoparticles were affected only slightly by the ablation time and fluence at a wavelength of 1064 nm, which was explained by a dynamic formation mechanism with surface charge effects. The nanoparticles formed by ablation at 355 nm had a distinctive wire-shape with a small diameter, which was attributed to a continuous fragmentation and formation mechanism.
▷ SongHee Han, Hyun Sik You, Sang Kyu Kim
"Comformer-specific Ionization Spectroscopy of Bromocyclohexane:
Equatorial versus Axial conformers"
J. Phys. Chem. A, 2010, 114, 10005-10010
Ionization of equatorial and axial conformational isomers of the chair-bromocyclohexane is investigated with use of the vacuum ultraviolet mass-analyzed threshold ionization (MATI) spectroscopic technique. Two distinct ionization energies of 9.8308 ± 0.0025 and 9.8409 ± 0.0025 eV are determined for equatorial
or axial conformers, respectively. From the conformer-selective vibrational analysis, it is found that the equatorial conformer undergoes a drastic structural change upon ionization especially along the C-Br distortion mode, whereas the axial conformer shows the modest change along the ring-puckering mode with ionization, corresponding to the reaction coordinate for the conformational interconversion. Density functional theory (DFT) calculations with and without considering the spin-orbit coupling provide the
appropriate mode assignments for the vibrational bands active in the ionization spectra. Natural bond orbital (NBO) analysis is carried out to give insights into the contribution of the anomeric effect to the structure-energy relationship in each conformational isomer.
▷ Ki Young Yeon, Dahyi Jeong, Sang Kyu Kim
"Intrinsic lifetimes of the Soret bands of the free base tetraphenylporphine (H2TPP) and
Cu(II)TPP in the condensed phase"
Chem. Commun., 46, 5572-5574 (2010)
Soret band lifetimes of the free-base tetraphenylporphine (H2TPP) and Cu(II) tetraphenylporphine (CuIITPP) at 408 nm have been directly measured with femtosecond (fs) resolution using the fluorescence-upconversion technique for the first time, giving τ = 68 ± 15 and 63 ± 15 fs,
respectively, in benzene
▷ Songhee Han, N. Jiten Singh, Tae Yeon Kang, Kyo-Won Choi, Sunyoung Choi,
Sun Jong Baek, Kwang S. Kim, Sang Kyu Kim
"Aromatic π-π interaction mediated by a metal atom: structure and ionization of the
bis(η6-benzene)chromium benzene cluster"
Phys. Chem. Chem. Phys., 12, 7648-7653 (2010)
Aromatic π–π interaction in the presence of a metal atom has been investigated experimentally and theoretically with the model system of bis(η6-benzene)chromium–benzene cluster (Cr(Bz)2–Bz) in which a free solvating benzene is non-covalently
attached to the benzene
moiety of Cr(Bz)2. One-photon mass-analyzed threshold
ionization (MATI)
spectroscopy and first principles calculations are employed to identify the structure of Cr(Bz)2–Bz which adopts the parallel-displaced configuration. The decrease in ionization potential for Cr(Bz)2–Bz compared with Cr(Bz)2, resulting from the increase of the cation–π stabilization energy upon ionization, is consistent with the parallel-displaced structure of the cluster. Theoretical calculations give the detailed cluster structures with associated energetics, thus revealing
the nature of π–π–metal or π–π–cation
interactions at the molecular level.
▷ Jeong Sik Lim, Sang Kyu Kim
"Experimental probing of conical intersection dynamics in the photodissociation of thioanisole"
Nature Chemistry, 2, 627-632 (2010)
Direct experimental probing of conical intersections is rare but here, in studies of the photodissociation of thioanisole, a striking dependence of the non-adiabatic transition probability on photoexcitation energy has been observed, revealing the nuclear configuration of the conical intersection and its dynamic role
in such transitions.
▷ Doo-Sik Ahn, So-Yeon Kim, Goo-Il Lim, Sungyul Lee, Young S. Choi, Sang Kyu Kim
"Mode-Dependent Fano Resonances Observed in the Predissociation of Diazirine in the S1 State"
Angew. Chem. Int. Ed., 49, 7, 1244-1247 (2010) (selected
as a VIP)
Lights, spectrometer, action: Crucial information about the detailed shape of the potential-energy surface in the vicinity of the transition state is obtained from the Fano resonances in the photodissociation cross-section of diazirine in the S1 state. The
excitation along the asymmetric C-N stretching mode accelerates the
ring-opening reaction, suggesting that two C-N bonds of the excited diazirine break in a stepwise manner (see scheme).
▷ Songhee Han, Tae Yeon Kang, Sang Kyu Kim
"Rotationally resolved spectroscopy of the 2A1 ← 2B1 transition of H2S+ above the barrier to linearity
using the mass-analyzed threshold ionization photofragment excitation technique"
J. Chem. Phys., 132, 124304 (2010)
The 2A1 ← 2B1 transitions of H2S+ above the barrier to linearity have been investigated with the energy resolution high enough to identify individual rotational transition lines for the first time. The rotational cooling of the cation is achieved either by the direct ionization or mass-analyzed threshold ionization (MATI) technique employed in the vacuum-ultraviolet laser excitation of the jet-cooled
H2S. Subsequent photoexcitation leads to the H2S+ → H2 + S+ dissociation and the S+ product yield taken as a function of the excitation energy gives the photofragment excitation (PHOFEX)
spectra. The combined use of MATI and PHOFEX techniques greatly simplifies the spectrum allowing the accurate identification of the rotationally resolved bands which is otherwise a formidable task due to the intrinsic complexity of the 2A1 ← 2B1 transition. Highly excited states of (0,7,0), (0,8,0), and (0,9,0) vibronic levels with different K quantum numbers which are located above the barrier to linearity are thoroughly investigated. The bent-to-quasilinear transition of H2S+ above the barrier to linearity shows the characteristics of the Renner–Teller effect, showing the large A rotational constant and strong intensity borrowing of the highly vibrationally excited ground levels such as (0,23,0) or (0,24,0) in the dipole-allowed excitation. Spectroscopic parameters of term values, rotational, and spin-orbit coupling constants are precisely determined in this work, providing the most quantitative spectroscopic
structure of the H2S+ to date. Quantum-state dependent photodissociation dynamics are also discussed from spectral features of PHOFEX.
Oleg Kostko, Sang Kyu Kim, Stephen R. Leone, Musahid Ahmed, "Mass-Analyzed Threshold Ionization (MATI) Spectroscopy of Atoms and Molecules Using
VUV Synchrotron Radiation", J. Phys. Chem. A, 113, 14206-14211 (2009).[PDF]
Jeong Sik Lim, Heechol Choi, Ivan S. Lim, Seong Byung Park, Yoon Sup Lee,
Sang Kyu Kim, "Photodissociation Dynamics of Thiophenol-d1: The Nature of Excited Electronic States along the S-D Bond Dissociation Corrdinate", J.
Phys. Chem. A, 113, 10410-10416 (2009).[PDF]
Kyoung-Seok Lee,
Ki Young Yeon, Kyung-Hoon Jung,
Sang Kyu Kim, "Direct observation of the primary and secondary C-Br bond cleavages from the 1,2-dibromopropane photodissociation at 234 and 265 nm using the velocity map ion imaging technique", J.
Phys. Chem. A, vol.112, 9312-9317 (2008).[PDF]
Kyo-Won Choi, Sunyoung
Choi, Doo-Sik Ahn, Songhee Han, Tae Yeon Kang, Sun Jong Baek, Sang Kyu Kim, "Clustering dynamics of the metal-benzene sandwich
complex: the role of microscopic structure of the solute in the bis(η6-benzene)chromium·Arn clusters (n=
Phys. Chem. A, 122, 7125-7127 (2008).[PDF]
Doo-Sik Ahn,
Kyo-Won Choi, Sun Jong Baek, Young S. Choi, Sungyul Lee, Heechol Choi, Kyoung
Koo Baeck, Sang Kyu Kim, "Structure of Pyridazine in the S1 state:
Experiment and Theory", ChemPhysChem, 9, 1610-1616 (2008)[PDF]
Choi, Kyo-Won Choi, Songhee Han, Doo-Sik Ahn, Tae Yeon Kang, Sun Jong Baek, Sang
Kyu Kim, "Conformationally specific vacuum-ultraviolet mass-analyzed
threshold ionization spectroscopy of alkanethiols: structure and ionization of
conformational isomers of ethanethiol, isopropanethiol, 1-propanethiol,
tert-butanethiol, and 1-butanethiol", J.
Phys. Chem. A, 122, 7191-7199 (2008).[PDF]
Doo-Sik Ahn, Jeongmook Lee,
Jeong-Mo Choi, Kyoung-Seok Lee, Sun Jong Baek, Kunhye Lee, Kyoung-Koo Baeck,
Sang Kyu Kim, "State-selective predissociation dynamics of methylamines: the
vibronic and H/D effects on the conical intersection dynamics", J. Chem.
Phys., 128, 224305 (2008).[PDF]
Choi, Tae Yeon Kang, Kyo-Won Choi, Songhee Han, Doo-Sik Ahn, Sun Jong Baek, and
Sang Kyu Kim, "Ionization spectroscopy of conformational isomers of
propanal: the origin of the conformational preference", J. Phys. Chem. A., 112, 5060–5063 (2008).[PDF]
Songhee Han, Tae Yeon
Kang, Sunyoung
Choi, Kyo-Won Choi,
Sun Jong Baek, Sungyul Lee
Sang Kyu Kim, "One-photon ionization spectroscopy of jet-cooled
oxazole and thiazole: the role of oxygen and sulfur in the π-conjugation of
heterocyclic compounds" Phys.
Chem. Chem. Phys., 10, 3883 – 3887 (2008).[PDF]
Hoon Han,
Seong Byeong Park, Sang Kyu Kim, and Sukbok Chang, "Copper-Nitrenoid Formation and Transfer in Catalytic Olefin Aziridination
Utilizing Chelating 2-Pyridylsulfonyl Moieties", J. Org. Chem., 73, 2862
Jeong Sik Lim, Yoon Sup Lee, and Sang Kyu Kim, "Control of the Intramolecular orbital alignment observed in the photodissociation of thiophenol: the conformational manipulation via the chemical substitution", Angew.
Chem. int. ed., 47, 10, 1853-1856 (2008) (selected as a VIP). [PDF]
Ho-Sung Kim, Doo-Sik Ahn, Sang-Yoon Chung, Sang Kyu Kim, SungyulLee, "Tautomerization of adenine facilitated
by water: Computational study of microsolvation", J. Phys. Chem. A, 111 (32),
Kyo-Won Choi, Doo-Sik Ahn, Joo-Hee Lee, and Sang Kyu Kim, "A conformationally specific alpha- and beta-alanine decarboxylation pathway", Chem. Commun. (9) 1041, (2007). [PDF]
Ivan S. Lim, Jung Sik Lim, Yoon Sup Lee, and Sang Kyu Kim, "Experimental and theoretical study of photodissociation reaction of thiophenol at 243 nm: observation of the intramolecular orbital alignment", J. Chem. Phys., 126, 034306, (2007). [PDF]
Kyo-Won Choi, Sunyoung Choi, Sun Jong Baek and Sang Kyu Kim, "Pulsed-field ionization spectroscopy of high Rydberg states (n = 50-200) of Bis(η6-benzene)chromium", J. Chem. Phys., 126, 034308, (2007). [PDF]
Sunyoung Choi, Kyo-Won Choi, Sang Kyu Kim, Sangyoon Chung, and Sungyul Lee, "Vibrational Structures of Dimethyl sulfide and Ethylene sulfide cations studied by Vacuum-UV mass-analyzed threshold ionization (MATI) spectroscopy" J. Phys. Chem. A, 110, 13183, (2006). [PDF]
Ji Min Lee, Doo-Sik Ahn, Doo Young Jung, Junseung Lee, Youngkyu Do, Sang Kyu Kim, and Sukbok Chang, "Hydrogen-Bond-Directed Highly Stereoselective Synthesis of Z-Enamides via Pd-Catalyzed Oxidative Amidation of Conjugated Olefins", J. Am. Chem. Soc., 128, 12954, (2006). [PDF]
Jeong Sik Lim, Ivan S. Lim, Kyoung-Seok Lee, Doo-Sik Ahn, Yoon Sup Lee, and Sang Kyu Kim, "Intramolecular orbital alignment observed in the photodissociation of thiophenol-d1", Angew. Chem. int. ed., 45, 6290, (2006) [PDF]
Min Hee Park, Kyo-Won Choi, Sunyoung Choi, and Sang Kyu Kim, "Vibrational structures of methylamine isotopomers in the predissociative à states: CH3NHD, CD3NH2, CD3NHD, and CD3ND2", J. Chem. Phys., 125, 084311, (2006) [PDF]
Kyo-Won Choi, Doo-Sik Ahn, Joo-Hee Lee, Sang Kyu Kim, "Vibrational Spectroscopy of the Pyridazine Cation in the Ground State", J. Phys. Chem. A., 110 (8), 2634, (2006). [PDF]
Kyoung-Seok Lee, Jung-Sik Lim, Doo Sik Ahn, Kyo-Won Choi, Sang Kyu Kim, Young S. Choi, "Nonadiabatic Dynamics in the Photodissociation of ICH2CN at 266 and 304 nm Using a Velocity Map Ion Imaging Technique", J. Chem. Phys., 124, 124307,
Kyo-Won Choi, Joo-Hee Lee, Sang Kyu Kim, "Vacuum-Ultraviolet Ionization Spectroscopy of the Jet-Cooled RNA-Base Uracil", Chem. Commun., 1, 78, (2006). [PDF]
Kyo-Won Choi, Joo-Hee Lee, Sang Kyu Kim, "Ionization Spectroscopy of a DNA Base: Vacuum-Ultraviolet Mass-Analyzed Threshold Ionization Spectroscopy of Jet-Cooled Thymine", J. Am. Chem. Soc.(Communication), 127, 15674, (2005). [PDF]
In-Sun Jeon, Doo-Sik Ahn, Sung-Woo Park, Sungyul Lee, and S. K. Kim, "Structures and isomerization of serine in aqueous solution: Computational study", Chem. Phys. Lett., 403, 72-76 (2005). [PDF]
Doo-Sik Ahn, Ae-Ri Kang, Sungyul Lee, Bongsoo Kim, Daniel Neuhauser, and S. K. Kim, "On the stability of glycine-water clusters with excess electron: Implications for photoelectron spectroscopy", J. Chem. Phys., 122, 84310 (2005). [PDF]
Kyo-Won Choi, Doo-Sik Ahn, Sungyul Lee, and S. K. Kim, "One-Photon Mass-Analyzed Threshold Ioniization Spectroscopy of Bis(η6-benzene)chromium and Its benzene and Ar Clusters", J. Phys. Chem. A, 108, 11292-11295 (2004). [PDF]
K.-W. Choi, D.-S. Ahn, S. Lee, H. Choi, K.-K. Baeck, S.-U. Heo, S. J. Baek, Y. S. Choi, and S. K. Kim, "Structural Distortion of Pyridazine in the 1(n,π*) Excited State: Evidence for Local Excitation", Chem. Phys. Chem., 5, 737-739 (2004). [PDF]
S. Y. Chae, M. K. Park, S. K. Lee, T. Y. Kim, S. K. Kim, and W. I. Lee, "Preparation of size-controlled TiO2 nanoparticles and derivation of optically transparent photocatalytic films", Chem. Mater., 15, 3326-3331 (2003). [PDF]
Y. Masumoto, S. K. Kim, T. Suzuki, "Femtosecond photoelectron imaging study of pyridazine: S1 lifetime and (3s,3p) Rydberg state energetics", J. Chem. Phys., 119 (1), 300-303 (2003). [PDF]
S. J. Baek, K.-W. Choi, Y. S. Choi, and S. K. Kim, "Spectroscopy and dynamics of methylamine II: rotational and vibrational structures of CH3NH2 and CH3ND2 in cationic D0 states" J. Chem. Phys., 118 (24), 11040-11047 (2003). [PDF]
S. J. Baek, K.-W. Choi, Y. S. Choi, and S. K. Kim, "Spectroscopy and dynamics of methylamine I: rotational and vibrational structures of CH3NH2 and CH3ND2 in à states" J. Chem. Phys., 118 (24), 11026-11039 (2003). [PDF]
S. J. Baek, K.-W. Choi, Y. S. Choi, and S. K. Kim, "First excited and cationic ground states of jet-cooled 2-aminopyridines · Arn (n=1,2) clusters: energetics and structures", J. Phys. Chem. A, 107 (24), 4826-4828 (2003). [PDF]
S. J. Baek, K.-W. Choi, Y. S. Choi, and S. K. Kim, "Vibrational structures of predissociating methylamines (CH3NH2 and CH3ND2) in à states: Free internal rotation of CH3 with respect to NH2", J. Chem. Phys., 117 (22), 10057 (2002). [PDF]
S. J. Baek, K.-W. Choi, Y. S. Choi, and S. K. Kim, "Resonant-enhanced two-photon ionization and mass-analyzed threshold ionization spectroscopy of jet-cooled 2-aminopyridines (2AP-NH2, -ND2, -NHD, and -NDH)", J. Chem. Phys., 117(5), 2131-2140 (2002). [PDF]
S. J. Baek, D. Lee, K.-W. Choi, Y. S. Choi, and S. K. Kim, "Torsional vibrational levels combined with higher frequency modes of the jet-cooled p-methoxybenzyl alcohol in the S1 excited state", J. Mol. Structure, 611(1-3), 203-211 (2002). [PDF]
T. S. Kim, K.-W. Choi, S. K. Kim, Y. S. Choi, S. W. Park, D. S. Ahn, S. Lee, and K. Yoshihara, "Fluorescence excitation spectroscopy of octatetraene-Xe van der Waals clusters", Bull. Korean Chem. Soc., 23(2), 195-200 (2002). [PDF]
D. Lee, S. J. Baek, K.-W. Choi, Y. S. Choi, and S. K. Kim, "Resonantly-enhanced two-photon ionization and mass-analyzed threshold ionization (MATI) spectroscopy of 2-hydroxypyridine", Bull. Korean Chem. Soc., 23(2), 277-280 (2002). [PDF]
W.-H. Park, S. H. Cho, H. Cho, S. K. Kim, and Y. S. Choi, "Ultraviolet Photolysis of 1,6-Methano[10]annulene Generates the Singlet Methylene", Bull. Korean Chem. Soc. 22(9), 1030-1032 (2001). [PDF]
S. K. Shin, S. K. Kim, H. L. Kim, and C. R. Park, "Two photon dissociation of acetone, acetaldehyde, and acetic acid at 243 nm: translational energy release in the H atom channel", J. Photochemistry and Photobiology A: Chemistry 143, 11-16 (2001). [PDF]
H. T. Kwon, S. K. Shin, S. K. Kim, H. L. Kim, and C. R. Park, "Photodissociation dynamics of acetic acid and trifluoroacetic acid at 193 nm", J. Phys. Chem. A 105 (28), 6775-6779 (2001).[PDF]
S. T. Park, S. K. Kim, and M. S. Kim, "Vacuum-ultraviolet mass-analysed threshold ionization spectra of iodobutane isomers: conformer-specific ionization and ion-core dissociation followed by ionization", J. Chem. Phys. 115 (6), 2492-2498 (2001).
S. T. Park, S. K. Kim, and M. S. Kim, "One-photon mass-analysed threshold ionization spectroscopy of 1- and 2-iodopropanes in vacuum ultraviolet", J. Chem. Phys. 114 (13), 5568-5576 (2001). [PDF]
S. H. Cho, W.-H. Park, S. K. Kim, and Y. S. Choi, "Unimolecular dissociation dynamics of vinyl chloride on the ground potential energy surface: the method of excitation and product state distributions of HCl and Cl fragments",
J. Phys. Chem. A. 104(45), 10482-10488 (2000). [PDF]
M.-C. Yoon, S. J. Baek, H. Cho, Y. S. Choi, S. K. Kim, "Supersonic jet spectroscopic study of p-methoxybenzyl
alcohol", J. Phys. Chem. A. 104(45), 10173-10178 (2000). [PDF]
M.-C. Yoon, Y. S. Choi, S. K. Kim, "The OH product state distribution from the photodissociation of hexafloroacetylacetone", J. Phys. Chem. A, 104(19), 4352-4355 (2000). Chem. Phys. (Commu), 111, 456-459 (1999).
G.-I. Lim, S.-M. Lim, S. K. Kim,
and Young S. Choi, "Unexpectedly large O37ClO/O35ClO intensity ratios of the fluorescence from the low-energy vibrational levels of OClO (A2A2)", J. Chem. Phys. (Commu), 111,
M.-C. Yoon, Y. S. Choi, S. K. Kim,
"Photodissociation Dynamics of acetylacetone: the OH product state
distribution", J. Chem. Phys. 110, 11850-11855 (1999). [PDF]
S.-M. Lim, G.-I. Lim, T.-S. Kim, S.
K. Kim, Y. S. Choi, "Fluorescence excitation spectrum of OClO
(A2A2)", J. Phys. Chem. A, 103 (13),
2097-2099 (1999).
M.-C. Yoon, Y. S. Choi, S. K.
Kim, "Fluorescence excitation spectroscopic study of the jet-cooled acetyl
cyanide", J. Chem. Phys., 110, 7185-7191
G.-I. Lim, M.-C. Yoon, S.-M. Lim, T.-S. Kim, S. K. Kim, Y. S. Choi, I. Kwak, "Fluorescence excitation spectroscopy of the jet-cooled dimethyldiazirine: the CH3 torsional mode assignment", Bull. Korean Chem. Soc., 20(3), 365-366 (1999).
M.-C. Yoon, Y. S. Choi, S. K. Kim, "The OH production from the π-π* transition of acetylacetone", Chem. Phys. Letters, 300, 207 (1999). [PDF]
T.-S. Kim, S. K. Kim, Y. S. Choi, I. Kwak, "Laser-Induced Fluorescence Spectroscopy of the S1-S0 (1B2-1A1) Transition of Dimethyldiazirine", Bull. Korean Chem. Soc. 19, 1042 (1998).
S.-M. Lim, T.-S. Kim, G.-I. Lim, S. K. Kim, Y. S. Choi, "Direct formation of CH2(b1B1) in the near-UV photodissociation of diazirine", Chem. Phys. Letters 288, 828 (1998).[PDF]
T.-S. Kim, S. K. Kim, Y. S. Choi, I. Kwak, "On
the second electronic state near the S1 state in
dimethyldiazirine",J. Chem. Phys. 107, 8719
E. A. Wade, H. Clauberg, S. K. Kim, A. Mellinger, C. B. Moore, "Dynamics of Rotational Energy Release for Dissociation of Singlet Ketene and the Singlet/Triplet Branching Ratio", J. Phys. Chem. A 101, 732 (1997). [PDF]
S. K. Kim, E. R. Lovejoy, C. B. Moore, "Dynamics
at Unimolecular Transition States", in Gas-Phase Chemical
Reaction Systems: Experiments and Models 100 Years after Max Bodenstein, ed. by J. Wolfrum, H.-R. Volpp, R. Rannacher, J. Warnatz, Springer Series in Chemical
Physics No.61 (Springer Berlin, Heidelberg, 1996) p.67.
S. K. Kim, J. Guo, J. S. Baskin, A. H. Zewail,
"Femtosecond Chemically Activated Reactions: Concept of Nonstatistical Activation at High Thermal Energies", J. Phys. Chem. 100,
9202 (1996).
S. K. Kim, A. H. Zewail,
"Femtosecond elementary dynamics of transition states and asymmetric α-cleavage in Norrish reaction", Chem. Phys. Letters 250, 279
A. Douhal, S. K. Kim, A. H. Zewail, "Femtosecond molecular dynamics of tautomerization in model base pairs", Nature 378, 260 (1995). [PDF]
S. K. Kim, S. Pedersen, A. H. Zewail, "Direct Femtosecond Observation of the Transient Intermediate in the α-Cleavage Reaction of (CH3)2CO to 2CH3 + CO: Resolving the Issue of Concertedness", J. Chem. Phys. 103, 477 (1995). [PDF]
S. K. Kim, J. J. Breen, D. W. Willberg, L. W. Peng, A. Heikal, J. A. Syage, A. H. Zewail, "Solvation Ultrafast Dynamics of Reactions 8: Acid-Base Reactions in Finite-Sized Clusters of Naphthol in Ammonia, Water, and Piperidine", J. Phys. Chem.
S. K. Kim, S. Pedersen, A. H. Zewail, "Femtochemistry of Organometallics: Dynamics of Metal-Metal and Metal-Ligand Bond Cleavage in M2(CO)10", Chem. Phys. Letters 233, 500 (1995). [PDF]
S. K. Kim, E. R. Lovejoy, C. B. Moore, "Transition-State Vibrational Level Thresholds for the Dissociation of Triplet Ketene", J. Chem. Phys. 102, 3202 (1995). [PDF]
S. K. Kim, J.-K. Wang, A. H. Zewail, "Femtosecond pH jump: Dynamics of Acid-Base Reactions in Solvent Cages",
Chem. Phys. Letters 228, 369 (1994). [PDF]
E. R. Lovejoy, S. K. Kim, C. B. Moore, "Observation of Transition-State Vibrational Thresholds in the Rate of Dissociation of Ketene", Science 256, 1541 (1992). [PDF]
E. R. Lovejoy, S. K. Kim, R. A. Alvarez, C. B. Moore, "Kinetics of Intramolecular Carbon Atom Exchange in Ketene", J. Chem. Phys. 95, 4081 (1991). [PDF]
S. K. Kim, Y. S. Choi, C. D. Pibel, Q.-K. Zheng, C. B. Moore, "Determination of the Singlet/Triplet Branching Ratio in the Photodissociation of Ketene", J. Chem. Phys. 94, 1954 (1991). [PDF]
C. B. Moore, Q.-K. Zheng, Y. S. Choi, W. H. Green, S. K. Kim, A. J. Mahoney, W. H. Miller, C. D. Pibel, W. F. Polik, P. Teal, "The High-Resolution Spectroscopy of Dissociating Molecules", Phil. Trans. R. Soc. Lond.
S. K. Kim, M. S. Kim, S. W. Suh, "Surface-Enhanced Raman Scattering (SERS) of Aromatic Amino Acids and their Glycyl Peptides", Journal of Raman Spectroscopy 18, 171 (1987).
S. K. Kim, T. H. Joo, S. W. Suh, M. S. Kim, "Surface-Enhanced Raman Scattering (SERS) of Nucleic Acids: Adenine Series", Journal of Raman Spectroscopy 17, 381 (1986).
K. W. Kim, S. K. Kim, M. S. Kim, S. W. Suh, "Raman Spectroscopic study of 5'-rGMP sol", Biopolymers 25, 753 (1986).
S. B. Hong, S. K. Kim, M. S. Kim, S. W. Suh, "The Preliminary X-ray and Raman Study of GramicidinS:HCl", Archives of Biochemisty and Biophysics 243, 563 (1985).
S. K. Kim, M. S. Kim, S. W. Suh, "Kinetics of Hydrogen/Deuterium Exchange in 8-CH of 5-rAMP", Bulletin of Korean Chemical Society 6, 270 (1985).


text:
HUNTSVILLE, Alabama -- It would be interesting to know how many Huntsville-area fans purchased Crosby, Stills & Nash songs on iTunes the day after the folk-rockers' impressive Von Braun Center show on May 22.
CSN played some interesting newer material, including the cinematic "Burning for the Buddha." But it was their durable '60s and'70s hits that had the Mark C. Smith Concert Hall crowd singing along like it was an electric church.
Which of the band's classics did you enjoy hearing most at the Huntsville show? Let us know by voting in the below poll.

subset: commoncrawl


text:
Around The Web
Neato! Bubble wrap, now with new and updated square pattern!
Sigh. Seriously, I once opined that Marion could wear a burlap sack and still look fantastic. I have just been proven wrong.
Honestly, I love it! It's like sexy chainmail, which I can always get behind.
Maybe she'sknocked up.
I think it is the shoes that look cheap. She can work the dress.
It's not OMGWTFBBQ terrible, I think, but it's not the most flattering thing she's ever worn, either in colour or cut. More of a le blah.
i love you whatever you wear , Marion!!!!!!!!!
I don't know what's up with her boob situation, but higher neck lines like thatt end up having the opposite effect of modesty- it ends up looking like you're trying to burst out your outfit. I hope she didn't get work done…
The fabric does look a little cheap, but that nor the capesleeve bother me so much. It's really the shoes and Flock of Seagulls hair that turn me off to this look. She's got nice legs, but ankle straps don't really flatter her very much.
Is this still a Halloween costume photo? Because it's clearly an homage to her favorite old school stock Star Trek character — The Alien Babe Who Seduces Kirk. Both the dress and the 'do. I don't know why she didn't go all the way and do the skin makeup. Maybe she couldn't decide whether to go green or blue or grey or…
awfulplasticsurgery reckons she's had a boob job. I was sceptical at first, but now I'm thinking they might be on to something.
I think the sleeve (and/or maybe the way she's standing) is pulling the top of the dress wonky and thus making her look a little lopsided. I know this isn't exactly an "unfug it up," but lose the sleeve and change the shoes for maybe some slingbacks and it would look a bit retro.
Gaaah. The fabric looks strange and not nice to the touch. If you cover up the capesleeve, it is almost passable. Cover the sleeveless side, and it IS an old school Star Trek look.
In any case, the girl who played The Little Sparrow so well deserves better.
I hate it. Honestly, aside from the Oscar dress, I've never liked anything she's worn.
Also? I wore those shoes to prom in 1998.
Speaking of prom, it kind of looks like something you'd buy in the prom section at the nicest store in the worst mall in town. Not that that's bad, I mean that is where I shopped for my prom, and I probably looked at things in that exact fabric. But my prom was in the 90s and this is the new millenium!
I like the shoes, they make her feet and ankles look pretty.
I'm reeling from the thought that Marion might've gotten such an obvious boob job. That would make me almost as sad as Christina Hendricks going on a diet.
That said, everything about this looks cheap, from the shoes to the lipstick. And I think I saw Phoebe wearing those shoes in a "Charmed" episode. Oh, Marion. You can do so much better.
Total Star Trek, down to the Vulcan hairdo.
She's above this.
Her face is still fabulous though. And the color of the dress matches/accentuates her eyes, which could have been part of The Plan.
Horrible horrible Christmas bridesmaid shoes. Horrible.
How can you possibly be out of Diet Coke? I would drag my tired ass to a grocery store the next county over at midnight rather than run out of Diet Coke!!! I am so, so sorry.
Bras can work wonders, but these photos raise some questions:
Is she working on a remake of "Logan's Run"?
It looks like Marion is one pair of footed tights and a set of "dance paws" away from doing a moving and heartfelt modern dance interpretation of the theme from Star Wars.
I really hate the dress, so it's a testament to how awesome Mario Cotillard is that I still think she looks fabulous overall.
You know what this reminds me of? Grease. When Frenchie and Frankie Avalon sing their song the girls in the background are dressed exactly like this.
So classy, so sexy, so elegant!
I want to like it.
I want to hate it.
Weird hair do. But kind of Blade Runnerish which is cool and she pulls it off.
Weird disco dress but ooooooo shiny!
Shoes that don't really go with the dress but at least they are all matchy-matchy.
Capey mono sleeve but points for being not boring.
And so on…my brain keeps getting stuck all wibbly wobbly and I just can decide.
I think she's been corrupted, ie, Americanized. I think she went and ruined herself with a boob job, and not such a good one. She should have stayed French and slightly remote for a few more years, then made the plunge to outfits like this and surgery like that. I don't like this look at all.
First, let's deal with the real emergency … out of Diet Coke?!?! For god's sake woman – get the hence to a 7-11, McDonalds, Albertsons! Do what it takes before the crisis point is reached.
Now, as for the fashion emergency … I am done – DONE I tell you – with the one sleeve. I am getting a giant pair of scissors (like they use for ribbon cuttings), and I will be trolling the countryside looking for wrongs to right in realm of one-sleeveness.
I just realized why I want to talk like a night of the Round Table – it's this freaking chainmail dress. FUG.
It's just so generic. The shoes look payless from 1996. The dress looks cheap and ordinary. She looks blah. What happened to her fashion balls?
This look would be complete if she had nylons on, the kind with the reinforced toe.
I think she got breast implants. They make it harder to dress up because most clothes are cut for more average-breasted people. So, she wound up wearing something that fits up top but doesn't fit around her waist and hips.
I think a big problem is the lack of fit. I'd like to see the dress on someone with the body type it was cut for before I judge it.
Marion should buy clothes cut for her body.
i think she's got 2 helium balloons underneath that dress, leftover from kim kardashian's 130 30th birthday partays. the boobins make her look our of proportion now, head to toe. the wonky dress exaggerates the wonk further. great legs, though!
@Jeni, exactly! Her hair is even evoking the pyramid of rollers! Good call.
For whatever reason I was scrolling up from the bottom when I first saw this picture. I saw the dress, went past the face quickly, was forming a "thumbs down" opinion, and then saw the title. "Oh," I said to myself, "Marion Cotillard. She's good at this fashion thing. I better look again." Alas, even Marion C. couldn't save this dress IMHO.
if you watch some of marion's early films, she's definitely always had big tits. nsfw – http://tinyurl.com/388b5vj she may be filling out in her age, but if you watch nine they were fairly sizeable there as well.
maybe she's pregnant!
Well. Now I'm going to spend all night trying to figure out how to pronounce "L'yucky."
Anyway, this dress would work if you were to:
a) remove the monosleeve
b) make the dress fit better. Less baggy. Et Cetera.
The dress is made from the thin padding you get under cheap carpet, spray painted silver.
Dolly Parton meets Herman Munster-Yuck!!!
Looking at her previous pics, I think she just has really large, NATURAL boobs, which means after 30 it all comes down to the bra.
Wear a firm cupped bra, or a good strapless one a size too small, and the puppies will be up to your chin. No bra and they're just kind of…there.
As a DD in her 30′s I deal with the exact same thing every day. They look enormous (and nearly fake) on a "good" day, more like a B-cup when I'm doing laundry.
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Wow, this was a really quality post. In theory I'd like to write like this too – taking time and actual effort to make a good post… but what can I say… I procrastinate alot and never appear to get something done.
She is looking gorgeous in this dress. I do have such a dress.
She looks adorable. She IS adorable. I love her dressed in this mignon little 60′s go-go dress. I love her dressed in jeans and a t-shirt. I love her dressed in a smart apron of cocoa leaves. J'adore cette fille.
I like everything about it except the sleeve. Rip it off and it would be excellent.
thanks you I like everything about it except the sleeve. Rip it off and it would be excellent.
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I do not like this shirt.But I like her hair.
Scrolldown fug! Bargain basement stripper reject shoes!!
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City of Quincy Hours Changing for Easter Holiday
With the Easter holiday coming this week the City of Quincy has revised their hours. The Quincy City Hall will be closed this Friday, April 3, 2015 in observance of Good Friday. City Hall will reopen Monday, April 6, for regular business hours.


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The Oregon Employment Department recently weighed the impact of winter tourism, just in time for the the close of this year's ski season. Its analysis combines federal jobs data and a statewide economic study.
While summer is still a larger draw for Oregon, there are signs the tourism industry is faring well in the winter, too.
The lack of on-mountain lodging makes Oregon's snowsports industry unique -- and gives a boost to nearby towns, according to the report. In Bend, lodging taxes reached a new peak in December.
Tourism employment is lumped into Oregon's leisure and hospitality industry, which grew 1.4 percent between December 2011 and December 2012, according to the report.
It points to a University of Oregon and ECONorthwest study that estimates skiing and other sports support 6,800 jobs in the state. Altogether, the industry makes a $481 million impact on the economy, that survey shows.
--Molly Young


text:
Editor's note: Christine Robere is the president of United Way of the Lakeshore, serving Muskegon, Newaygo and Oceana counties.
The United Way is trying to raise almost $2.7 million in Muskegon County by mid-November, and $90,000 each in Newaygo and Oceana counties by early next year.
In this interview, Robere talks about the 2010-11 United Way campaign, how the recession has affected giving and, despite economic hardship, how people are still giving to help improve the quality of people's lives.
Download the MP3 or listen to the full interview.


text:
Fears Rise That More Than 8 Died In Snohomish County Mudslide
The search for survivors of a deadly Washington state mudslide grew Monday to include 108 names of people who were reported missing or were unaccounted for, but authorities cautioned the figure would likely decline dramatically.
Still, the size of the list raised concerns the death toll would rise far above the eight people who have been confirmed dead after the 1-square-mile slide Saturday swept through part of a former fishing village about 55 miles northeast of Seattle. Several people also were critically injured. About 30 homes were destroyed, and the debris blocked a 1-mile stretch of state highway.
"The situation is very grim," Snohomish County Fire District 21 Chief Travis Hots said, stressing that authorities are still in rescue mode and are holding out hope. But he noted: "We have not found anyone alive on this pile since Saturday."
Adding to the worries was that the slide struck Saturday morning, a time of the weekend when most people are at home. Of the 49 structures in the neighborhood hit by the slide, authorities believe at least 25 were occupied full-time.
Snohomish County emergency management director John Pennington said the list of 108 names was pulled together from various sources that authorities are working from, and it doesn't mean there are that many injuries or fatalities.
Among the possible missing are construction workers coming into the neighborhood and people just driving by.
"It's a soft 108," Pennington said. "The objective here is very clear. Let's consolidate the lists, consolidate the information, the data that we've got. Let's make it helpful to the families that are out that, that are really struggling right now."
Snohomish County urges residents to call 425-388-5088 to report missing persons or to report they're OK if they've been out of contact. Cell phone, radio and Internet connections were largely cut off in the area; however, laptops and a Wi-Fi connection were available at the Darrington library.
Pennington said crews are working to get communication back up and running.
"We have a Department of Transportation-type reader board that will have a radio signal that can spread out about two miles. It will be an AM radio station that you can tune into and get information from Snohomish County," he said.
Search and rescue teams took to the air in helicopters and the ground on foot with search dogs to look for anyone who might still be alive, but the possibility of additional slides limited their movement.
"There are concerns about additional slides in the same area that was affected on Saturday. As a result, some of the ground crew have been pulled back from that area," said Snohomish County sheriff's spokesperson Shari Ireton.
Airlift Northwest pilot Lucky Mertes, who helped evacuate some of the injured, said what he saw reminded him of the Mount St. Helens eruption more than 30 years ago.
"With the trees and the gash in the mountain, it's sort of what it reminded me of, but obviously not to that scale. But [it's] much bigger than you'd normally expect when you hear about a mudslide," he said.
The injured victims were taken to Harborview Medical Center in Seattle, mostly with crushing injuries. The victims includes a 6-month-old boy who arrived in critical condition.
Hospital spokeswoman Susan Gregg said some of the families of the missing came to the hospital.
"I think they just didn't know where to go and they figured that, you know, Harborview takes care of the most seriously injured, and they thought their loved one might be here," Gregg said.
Snohomish County sheriff's Lt. Rob Palmer said four bodies were discovered late Sunday. Earlier in the day, authorities said one body had been found on the debris field. Three people were already confirmed dead on Saturday.
Crews were able to get to the soupy, tree-strewn area that was 15-feet deep in places Sunday after geologists flew over in a helicopter and determined it was safe enough for emergency responders and technical rescue personnel to search for possible survivors, Hots said.
He added that they did not search the entire debris field, only drier areas safe to traverse.
Both frequent, heavy rainfall and geography make the area prone to landslides. Less than a decade ago, another slide hit in the same general area. Geologists and other experts said the Stillaguamish River likely caused some erosion in the area that was carved by glaciers.


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First Martin Corporation plans to bring a Marriott hotel brand to downtown Ann Arbor.
The Ann Arbor-based real estate company announced Thursday afternoon that Residence Inn by Marriott will anchor the proposed development at the corner of West Huron and North Ashley streets.
First Martin owns the property, which is now occupied by the Greyhound bus depot and the Ann Arbor Convention and Visitors Bureau.
The 110-room, extended-stay hotel will feature studio, one and two bedroom suites catered to longer stays.
"Residence Inn fits into the current downtown market in a balanced way," First Martin Vice President Mike Martin said in a statement. "It will add to what Ann Arbor has to offer as a whole and will be a catalyst for additional events and activities in the downtown area."
Residence Inn by Marriott has 653 hotels. According to the company's website:
For extended stays away from home, Residence Inn helps guests maintain a balance between work and life. Spacious suites with full kitchens combine home like comforts with functionality. Features like a complimentary hot breakfast and evening social hours make Residence Inn more home than hotel.
First Martin submitted a site plan in April for the hotel project. Plans call to construct a seven-level, mixed-use retail and hotel development, which will incorporate the bus depot facade and sign into the design.
Plans include ground-floor retail along the Huron Street frontage, and First Martin's Mike Martin said the retail use could be a restaurant with a sidewalk cafe.
Colliers International Ann Arbor is marketing the retail space for lease as an opportunity for a "landmark" restaurant.
Other ground level uses include a lobby, meeting rooms, office, exercise room, pool, patio, prep kitchen and laundry.
First Martin is working with architects Zivic & Hurdle and Hobbs & Black. The plans went before Ann Arbor's Design Review Board in January.
If plans are approved, the goal is to open the hotel in summer 2015.
"The selection of Residence Inn is the result of our careful approach to development," Martin said. "With half a century of financial and personal investment in Ann Arbor, we've been very deliberate in determining the right scale, time and partners for this development."
Lizzy Alfs is a business reporter for The Ann Arbor News. Reach her at 734-623-2584, email her email@example.com or follow her on Twitter.


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The Knicks are reportedly active in the days leading up to Thursday's NBA Draft at Barclays Center.
In addition to conducting pre-draft workouts, the Knicks—owners of the 24th overall pick—have also toyed with the idea of reacquiring the rights to last year's first-round pick, Kostas Papanikolaou, according to Marc Berman of the New York Post.
Papanikolaou was taken by the Knicks with the 48th overall pick last year and then traded to the Trail Blazers in the deal that brought Raymond Felton back to the Knicks.
According to sources, Portland has received offers for Papanikolaou from others teams with picks in the late 20s. It appears Portland GM Neil Oshey wants to wait until draft night to determine who is available. The Blazers believe if Papanikolaou were in this year's draft, he'd easily be a first-rounder.
"His strong desire is to play in the NBA next season," Cornstein told The Post yesterday. "He's won two straight Euroleague titles. If that can't happen in Portland, maybe it can happen somewhere else."
The 22-year-old Papanikolaou currently plays for Olympiakos and has a $1.1 million buyout. He's also regarded as a solid defender and shooter, having made over 50 percent of his 3-point attempts in Euroleague play.
The issue for the Knicks is that, according to Berman, the Blazers want the 24th overall pick, which the Knicks aren't technically permitted to trade (the NBA prohibits trading first-round picks in consecutive years). However, the deal could be put into place on draft night and then completed after June 30, when the Knicks would be able to deal the rights of whomever they acquired on Thursday.
Of course, the Knicks are going to be reluctant to relinquish a first-round pick for someone they acquired with the 48th overall pick a season ago, but the 6-8 Papanikolaou has supposedly improved.
The Knicks might also feel the pressure to acquire a lanky small forward because they could lose one of their own. As Berman wrote in another article, the New Orleans Pelicans (that's an NBA team) have taken a liking to Chris Copeland, the 28-year-old soon-to-be restricted free agent who shot well and defended poorly in his first NBA season.
According to an NBA source, the newly named New Orleans Pelicans are planning to make a strong bid for the 6-foot-9 sniper as they are well under the salary cap and can make an offer that will blow Knicks owner James Dolan out of the water.
The Knicks can match any Copeland offer since he is a restricted free agent, but only up to $3.1 million — their mini mid-level exception. Since the Pelicans are under the cap, they can easily top that number.
Berman wrote that Copeland wants "Steve Novak money," which was $16 million over four years.


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The trio get started praising the Freddy Awards presentation, which Owens calls "the Super Bowl of high school plays." They also discuss a dust-up among Easton businesses about the cost to participate as a vendor in the annual Heritage Day event. But it's talk about school property taxes that gets them riled up.
"Too few people actually get up off of their derriere and head out to school board meetings and raise their voices to be heard. And that's the problem," Owens says. "All (school boards) see is band parents who want new uniforms, and swim parents who want a new pool and football parents who, you know, want the best of everything. They don't see the people I hear from that are on a fixed income that really and truly don't know how they're going to pay these added costs, between health care and property taxes and trying to put food on the table."
Speaking of expenses, how about the price at the pump these days? What are the hosts driving? And Deegan shares a story that sends shivers up his spine.
Click the play button below to listen to this month's 30-minute installment, or download it here.
The hosts want your feedback. Post a comment below, or e-mail Owens or Deegan to respond.


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FORESTVILLE - The status quo was more or less maintained during the Forestville Board of Education's reorganizational meeting Thursday evening in the high school library.
Sylvester Cleary was unanimously approved to continue as board president for the 2013-2014 school year.
"I would like to thank my fellow board members because I really feel we have a very unique organization here in Forestville," Cleary said. "And it's attributed to all the dedication that you folks have. You folks make the president's job look easy. But, it's through your dedication and it's through your commitment and love of the kids that gives me the inspiration to keep going. I'm looking forward to this coming year for some great things out of this board."
Article Photos
OBSERVER Photo by Greg Fox
The status quo was more or less maintained during the Forestville Board of Education's reorganizational meeting Thursday evening. Both Sylvester Cleary and Carol Woodward were unanimously approved to continue on as president and vice president of the board, respectively.
A separate vote allowed Cleary to continue on as legislative liaison for the Chautauqua County School Boards Association.
Carol Woodward was also unanimously approved to continue on as vice president of the board. She also thanked her fellow board members for allowing her to serve in that regard.
One position that did change was the board clerk seat. After a unanimous vote, June Prince was given that role. She replaced Elenor Hebner, who retired at the previous meeting.
After reorganizing, the board unanimously approved the purchase of school buses at an estimated maximum cost not to exceed $224,000. The purchase was approved by voters as a proposition during the recent budget vote.
The board also approved a measure allowing the superintendent to enter into a contract with Silver Creek Central School for a shared transportation supervisor between the two districts. Silver Creek previously approved the measure on their end in a recent meeting.
As part of the reorganization, the Comprehensive District Educational Planning committee was eliminated from the list of committees for the upcoming school year.
"The reason for discontinuing the CDEP committee would be that the (Annual Professional Performance Review) legislation really has engulfed what was the bulk of the work for the committee," Superintendent Charles Leichner said. "It no longer meets, so I don't think we should fill it."
A budget committee, which was declared a committee of the whole, was formed to take the place of the eliminated task force. The negotiations, policy and audit and finance committees were kept in place.
At the end of the meeting, the board entered into executive session to discuss a matter dealing with collective negotiations pursuant to a contract.
The next board meeting is scheduled for Aug. 1 at 6 p.m. in the high school library.
Comments on this article may be submitted to firstname.lastname@example.com.


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Mary-Louise Klatt, who participates in a Michigan Humane Society program fostering animals until they are ready for adoption, said she suffered a heart attack in early March.
Joleen recognized something was wrong with her temporary master and began "barking and running back and forth," according to a statement by the Michigan Humane Society in Detroit.
The ruckus awoke Klatt's stepson who then checked found his stepmother was having a medical emergency and called for help.
"And she kept licking my face, trying to wake me up," said Klatt. "She's my angel!"
Once Klatt was released from the hospital, she decided she wanted to make Joleen a permanent part of her family.
The foster program places animals not ready for adoption, possibly because they are too young or recovering from illness, in homes until they can be placed permanently.
All costs are covered by the Michigan Humane Society In-Home Heroes foster program.


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A multi-vehicle crash in the outbound (eastbound) Squirrel Hill Tunnel temporarily shut down the tunnel Tuesday afternoon.
The closure caused a very long backup of traffic headed out of the city on Interstate 376 (Parkway East).
PennDOT said the tunnel was reopened shortly before 3:40 p.m.


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Huskies' Jerzerick picked for East-West squad
LEWISTOWN – Leadership, determination, hard work and solid character are the qualities needed to be a success in any endeavor, whether on the playing field, the classroom or the boardroom.
For Mifflin County's Curtis Jerzerick, these attributes have propelled him to high achievement on the football field and admittance into the United States Military Academy at West Point.
The accomplishments for the Husky senior are lengthy.
Jerzerick is senior class president and an Eagle Scout, Mid-Penn First Team all-star at tight end, honorable mention all Mid-Penn in basketball and a first-team District 6 Class AAAA all-star in basketball.
Add the East-West All-Star football game to his list of accomplishments.
Jerzerick is the first Mifflin County High School player selected to the game in the program's brief three-year history. He will suit up for the West team Sunday at 2 p.m. at Franklin Regional High School in Murrysville.
"I feel honored, but there are a lot of great athletes in Mifflin County. There are a lot of other guys on the team who could have been chosen," Jerzerick said. "When I found out I was selected, I was ecstatic, but I thought there are other players on my team who could be in my same position also.
"I'll be the first of many selected from Mifflin County for sure. We have some athletes working out in the weight room and some of the freshmen are looking to get some playing time next season. I'm looking for some of them to step it up."
In evaluating himself, Jerzerick believes the reason he was selected to the East-West game is his quickness.
"My strengths at TE (are that) I am a lot quicker off the ball so my first steps are faster than most D-lineman," he said. "Also, I'd say my footwork really created some of the holes that made my run blocking easier. I'm 185 pounds and to move 250-pound guys like I did was due to my footwork and then turning them instead of trying to knock them backward."
The East-West game is the icing on the cake to a football career that brought plenty of accolades and great memories for Jerzerick.
"My most proud moment in my high school career was holding up the district championship trophy with my teammates. That was great. That was the best day of my life right there, with all my brothers out in the middle of the field holding that trophy up. It was amazing," Jerzerick said. "Preparation was the key to my success more than anything else in high school and I think that will help me when I get to West Point. It's the main thing at West Point. If you are not prepared going in, you will fail."
Even though this will be his last high school game, Jerzerick is far from done with football. He will be taking his skills to play for the sprint team at Army.
Sprint football is considered a Division I sport at Army despite being a step down from the major college game. Sprint coach Mark West only recruits six athletes per year and Army has won the Sprint Football National Championship for two consecutive seasons. The Black Knights are in a league with Navy, Penn, Cornell, Princeton, Mansfield, CW Post, and Franklin and Pierce.
Jerzerick, who will major in environmental geography at West Point, is excited to get started.
"I want to a camp at Lafayette and a West Point sprint football coach was there. He immediately contacted me after camp," Jerzerick said. "My junior year in April we went on a day visit and it just felt like home. I knew I wanted to be there and now, since I was accepted, not a day goes by when I don't think about Army.
"Sprint football is a weight class football. It's 172-pounds and under. Also, you have to be hydrated every week. You have varsity football and right below it is sprint football," he explained. "Coach West wasn't sure what side of the ball I'll play on, but what stuck out to him was how I never gave up on a play. I think that comes from my Dad (Zane Jerzerick) right there telling me to never give up. I have to thank my dad for that more than anything."
Basic training begins July 2 and runs for six weeks. After basic, Curtis will head to sprint football practice with the season running from September to November. He will attend West Point for four years, come out with a bachelor's degree in science and be a commissioned officer.
To get into West Point is no small feat.
First, you must be nominated by either a congressman (a requirement) or one of the state's two senators. Congressman Tom Marino nominated Jerzerick. Second, the acceptance rate at West Point is only 9 percent, with more than 15,000 kids applying each year. In addition, Curtis had to have the grades, leadership skills and physical attributes as well.
Choosing the military path was practically a given for Jerzerick, who follows in the formidable footsteps of his two older brothers.
Louis enlisted in the Air Force and is stationed at Nellis AFB in Las Vegas, Nev. Julian graduated from the Naval Academy in 2013 with a degree in computer engineering and is a second lieutenant in the Marines Corps stationed at Camp Pendelton in California.
Their influence on Curtis is profound.
"I would like to make a career in the military. I don't see myself anywhere else," Jerzerick said. "It just fits me. It's home for me and seeing my brother (Louis) in his uniform and all the respect he gets. I would like to have that respect also."
His success and appointment is no surprise to Mifflin County football coach George Miskinis.
"Curtis is an outstanding individual and a three-year starter. He's always been very enthusiastic and he played with that enthusiasm and aggressiveness," Miskinis said. "He's developed into a real good leader. He holds everybody to the same standard he sets for himself. He is a great asset and will be missed.
"I think the East-West nomination is just the cherry on top of the sundae. Being selected is a great honor for him and his family. It's great for our program that he's the first one selected. He gets a chance to play among elite players in the state.
"Going to West Point is a 12 or 13 year accomplishment. It's about being disciplined and being a workout fanatic like he is. He sustained that self-discipline to workout when others were taking it easy. It's not just the physical its being mentally prepared. We've been blessed to have him. He's going to be a great leader for our country."
If, as Aristotle once said, you are what you repeatedly do, then achievement isn't an action you take but a habit you forge into your life. You don't have to seek out success. Harness the power of selected discipline to build the right habits, and extraordinary results will find you.
Curtis Jerzerick harnessed that discipline long ago, and success just keeps on finding him.


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Two Newark men were in stable condition this morning after they were shot and wounded at a Central Ward intersection late last night, police said.
Police responding to a shooting at South Orange Avenue and S. 9th Street shortly after 11 p.m., found a man with two gunshot wounds to the torso, said Detective Todd McClendon, a police department spokesman.
He said a short time later, a second man, who had been shot at the same intersection, showed up at the emergency room at University Hospital with a gunshot wound to the hip.
Their identities were not released.
McClendon said investigators have not yet determined a motive for the shooting.
Thursday night's shooting followed another shooting a day earlier, when a 26-year-old Union Township man was found dead in the driver's seat of a car on South 10th Street, McClendon said.
Wednesday's fatal shooting was the city's 17th homicide of the year and followed a spate of apparently unconnected shootings since Sunday that left three other men dead and more than a half dozen people wounded.
The recent increase in violence marked a departure from the beginning of the year, when Newark went 43 days without a murder, the longest stretch since 1961.


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STATEN ISLAND, N.Y. — The possibility that real estate and reality TV mogul Donald Trump will run for president isn't causing too many ripples among Staten Island Republicans.
"Ha!" City Councilman James Oddo (R-Mid-Island/Brooklyn) said of the possibility.
Trump has been getting a lot of press lately, saying that he might run as an independent if he doesn't get the GOP nod.
He has also caused a stir by resurrecting questions about whether President Barack Obama was born in the U.S. and is Constitutionally qualified to be president.
Such "birther" talk makes even many hard-core Obama-haters uncomfortable.
Oddo says that he's "looking for substance to 'trump' personality" in the White House race.
"If I want personality to that degree, I'll turn on the WWE," he said.
Despite Obama's poor poll ratings, Oddo said that it will take a formidable candidate to wrest the Oval Office from him.
"Obama may not wow you with charming stories at the dinner table," he said, "but you have to beat him on substance, on politics and policy."
State Sen. Andy Lanza (R-Staten Island) gives Trump credit for being fearless in "attacking every issue."
"I agree with a lot of the positions he's taken," said Lanza, pointing to Trump's takes on Libya, Egypt, national security issues and the economy.
"It resonates with me," he said. "It's good for the conversation."
But Lanza said that like GOP gubernatorial candidate Carl Paladino last year, Trump might be too gaffe-prone to be a serious contender.
"What works in the entertainment business might be a weakness in a campaign for the White House," he said. "To run for president, you have to demonstrate statesmanship and polish."
Lanza said that Trump embraces the birther issue at his own risk.
"It's risky to stake your candidacy on that," he said, "because it's so easily knocked out of the box. Then Trump would be done."
Oddo thinks that GOP Indiana Gov. Mitch Daniels could be the One for Republicans.
"I hope that Mitch Daniels throws his hat in the ring," he said. "He's absolutely a man of substance."
Daniels has been hailed for his education reform ideas and recently signed into law a bill that restricts teacher collective bargaining agreements.
The folks at the Independent Budget Office (IBO) can talk all they want about restoring the Staten Island Ferry fare, but former North Shore City Councilman Jay O'Donovan says that it won't be all that easy to do, even if the political will is there.
O'Donovan reminds us that the 1997 ferry fare elimination is set in law because it required an amending of the city administrative code. Another bill would have to pass the Council and be signed by the mayor in order to restore the 50-cent fare.
"That's the safeguard," the Democrat told us. "It can't be reinstated by fiat. You'd have to have hearings, public testimony, the works. And I don't think Mike Bloomberg would sign it."
O'Donovan said Mayor Rudolph Giuliani initially wanted to eliminate the fare by executive order, but that O'Donovan and others pushed for a law so that future mayors simply couldn't issue executive orders of their own restoring the fare.
O'Donovan started calling for the elimination of the fare when the city began pushing its free-transfer, "One City, One Fare" program.
To give the IBO a little breathing room: It's not that the group advocates restoring the fare (and cutting overnight service). As the group does every year, it recently issued a report suggesting those options as ways for the city to save money, giving the pros and cons for each.
However, the IBO is surely aware that even the faintest suggestion of such things is bound to cause a stir out here and give elected officials an easy opportunity for outrage.
The mounting national debt, the budget deficit and rising inflation have the U.S. "at the tipping point," says Rep. Michael Grimm (R-Staten Island/Brooklyn).
The seriousness of the situation was underlined by the Standard and Poor's rating service, which downgraded its outlook on U.S. credit to "negative" last week.
"That's very serious from where I sit," said Grimm. "It's a big message."
While the U.S. retained its blue-chip "AAA" credit rating, Grimm said that that could be downgraded soon enough if the country doesn't get its fiscal house in order.
Pointing to the nation's $14-trillion debt, Grimm said, "If we are not credit-worthy, the interest rate to service that debt goes up. It increases the problem."
Grimm said you don't need to talk to the experts to know that inflation is a threat that's looming bigger all the time and could push the economy into a new downward spin.
"The price of everything is going up," he said, "cereal, milk, bread, gasoline. It's real. You don't need a world-class economist to tell you that. Just talk to the people in the diner."
And the continuing devaluation of the dollar doesn't help, Grimm said.
"I'm very concerned about our monetary policy," he said. "We are at that tipping point."


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LACBC recently crowed that the 10% of Measure R (local return) funds set aside for cyclists & pedestrians became available. As LACBC puts it, the "collaborative effort between LACBC, LA Streetsblog (Damien Newton), and the Green LA Coalition"
led to the liberation of $3.27 million in funds for the next fiscal year for cycling and pedestrian projects.
However, anyone who was paying attention knows that those funds would have been $1.95 million, not $3.27 million, if it weren't for the efforts and scrutiny of one Bikeside board member – Stephen M Box.
When the "10% for bikes and peds" motion came before LA City Council Transportation Committee it was Stephen Box that noted that LADOT had calculated 10% incorrectly, first in City Watch and then in public comment:
The 10% commitment had advocates celebrating but a check of the math revealed a small $7.3 million problem, the LADOT had calculated the 10% on net funds yielding $10.8 million over the next 5 years instead of on gross which would yield $18.1 million.
LADOT used the net return, instead of the gross return, reducing the 10% commitment. Box mentioned this to the committee, and the Chief Legislative Analyst [CLA] (who some say is more powerful than the councilmembers themselves) agreed:
as I stood to leave, the City's Legislative Analyst (CLA) said "You're right." I waited but that was it. I asked "So then you'll fix it?" It was that simple. "Yes." Box's comment led to an increase of 68% in funding ( $18.1 / $10.8 = 1.68 ) from the 10% motion, which amounts to $1.32 million this year, and $7.3 million over 5 years.
It's all available online – check out the November 18th, 2009 meeting of the Transportation Committee meeting (99 Mb). Stephen's comment, and followup from staff, begin at 56:40.
LACBC – be honest with your narrative. You attribute the success to the efforts of three organizations, but 40% of the money ( [18.1 -10.8] / 18.1 ) can be attributed to Box's public comment, his City Watch article, and the CLA. Congratulations to Stephen Box and the CLA for freeing up $1.32 million in additional funds for cyclists and pedestrians for this (fiscal) year, and congratulations to the three org coalition (if indeed LACBC's narrative is accurate on that point) for the other $1.95 million.
(Edit – some may have trouble following the ball here. The $18.1 mil figure is for 5 years. It would have been $10.8 mil but for Box's efforts. That's 5 years. For this fiscal year, the amounts are $3.27 mil and $1.95. The "difference due to Box" is $7.3 mil over 5 years or $1.32 mil this year.)


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This spacious 3-bedroom pool villa is located in gated community of Golf Course in Kathu.
The villa has three bedrooms, all en-suite and one of the bedrooms also has an attached room that can be used as a study/play room etc. The master bedroom is huge and comes with walk in wardrobe and huge bathroom. Each bedroom overlooks the swimming pool.
In the large living and dining area, there is all new appliances and high quiality furniture. The kitchen is fully fitted with everything required to simply move in.
The whole villa has been very recently renovated and is completely re-painted. Every electrical item (including light fittings) have also been replaced to ensure you are renting a high quality home. The garden was also completely renovated at the same time.
The location is perfect for those with children at the nearby international school, yet is only 10 minutes from the beach.
6 Month Contract: THB 70,000 per month.
Long-term Rental Minimum Stay: 6.
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- Alberta NationTalk
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Quest-west Partnership Promotes Mineral Exploration
For Immediate Release
April 18, 2008
Office of the Premier
SMITHERS – The Province is supporting mineral exploration work in pine beetle-affected areas of the province with $6 million for Geoscience BC's QUEST West program, said Premier Gordon Campbell as he presented the funding to Geoscience BC at the Minerals North Conference today."Today we are building on the success of the QUEST project, which has resulted in 820,000 hectares of mountain pine beetle-infested forest being staked for mineral exploration," said Campbell. "QUEST West will continue this important geoscience research, help us to discover untapped mineral potential, attract new investment and support the economic diversification of pine beetle affected communities in B.C."
The new QUEST West funding will be used to generate new geoscience data, covering approximately 40,000 square kilometres extending from Vanderhoof-Fort St James to Terrace and including the communities of Fraser Lake, Burns Lake, Granisle, Houston, Telkwa and Smithers.
In June 2007, Geoscience BC, in partnership with the Province, launched the largest public geoscience project in the history of British Columbia. The $5 million QUEST (Quesnellia Exploration Strategy) program is producing geoscience information to help identify the untapped mineral potential beneath the mountain pine beetle-infested forests of British Columbia. Since the launch, the QUEST team has surveyed over 46,000 square kilometres in central B.C. Skyrocketing claims in QUEST's geophysical survey area demonstrate the exploration industry's interest in the area's potential for copper-gold mineral discoveries.
"The QUEST West Project will undertake a series of regional geoscience surveys designed to attract the mineral exploration industry into this region," said 'Lyn Anglin, president and CEO of Geoscience BC. "New geoscience data is key to attracting exploration interest, which will help to diversify the economy and ensure the sustainability of the region."
QUEST West is a partnership between the Province, Geoscience BC, the Northern Development Initiative Trust and communities through the Regional District of Bulkley-Nechako and the Terrace Economic Development Authority (TEDA). These partnerships will support QUEST-West geoscience projects.
"The QUEST West Project was identified as a priority project for the Regional District of Bulkley-Nechako because of the positive impacts this project can produce, including increased global competitiveness of our region, new mineral staking, increased exploration and ultimately the diversification of our economy," said Eileen Benedict, chair of the Regional District of Bulkley-Nechako. "The Regional District of Bulkley-Nechako is very confident about growth of the mining sector in our area and we look forward to beginning this exciting project with Geoscience BC."
The Northern Development Initiative Trust is providing the Regional District of Bulkley-Nechako with a grant of $750,000 to support the work of QUEST-West.
"New inventories of geoscience data are putting our region on the mining world's radar screen and we look forward to supporting exploration companies and new mine developments that will drive our economy forward," said Sharon Smith, mayor of Houston and Northern Trust board director.
The Northern Development Initiative Trust and the Regional District of Kitimat Stikine are also providing a grant of $10,000 to the Terrace Economic Development Authority who, along with $5,000 of their money in profits from last year's Minerals North Conference, will partner with Geoscience BC to reanalyze archived government stream sediment samples with modern geochemical analytical techniques.
"To be able to leverage the funds raised through our 2007 Minerals North Conference with Geoscience BC and the BC Geological Survey (BCGS) into the creation of a comprehensive data resource of the Terrace area for exploration companies has been exciting for us," said Lael McKeown, director of TEDA. "We would like to thank the Northern Trust, Geoscience BC and BCGS for their support of our projects."
The Ministry of Energy, Mines and Petroleum Resources, through the BC Geological Survey, will continue its support of QUEST-West by providing expertise and producing new geology maps and mineral deposit studies.
Established with a $25-million grant from the Province, Geoscience BC is an industry-led organization that conducts geoscience projects in partnership with industry, academia, government, First Nations and communities. Since 2005, Geoscience BC has led and/or funded a total of 38 geoscience projects valued at over $15 million.
British Columbia's mineral exploration activity reached a record high of nearly $416 million on 472 exploration projects in 2007. Of this, $170 million was spent on 144 projects in the northwest and nearly $95 million was spent on 88 projects in the central region of the province.
Media contact:
Bridgitte Anderson
Press Secretary
Office of the Premier
604 307-7177
'Lyn Anglin
President and CEO
Geoscience BC
604 290-1194
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- Irrigation doesn't increase corn yield – it captures it
- Apply enough water long enough
The proper use of irrigation can help corn producers capture the maximum amount of yield from improved hybrids.
IRRIGATION captures the maximum yield potential of improved corn hybrids.
When you're planting corn hybrids with the potential of yielding more than 600 bushels per acre, your irrigation focus should not be on increasing yield but rather on capturing it.
"In the last two years in Georgia, we've averaged about 180 bushels of corn per acre," says Dewey Lee, University of Georgia small grains agronomist. "And the reason that trend line is so sharp is because of irrigation."
And while irrigation might not have been much of a factor during the rain-filled summer of 2013, it is in most years.
"With irrigation, we're able to avoid some of the stresses that limit yield potential, and that's what we have to do. Irrigation is a tool in managing the corn plant to capture maximum yield. We don't increase yield, but we capture it," says Lee.
It's important, he says, the growers learn about the physiology and development of the corn plant. "When you know how this crop grows, you'll actually learn what inputs are necessary, and what you can do to maintain yield potential. It's up to us how to use water."
One-inch of water in the life of a crop can easily return 8 or 9 bushels of corn, says Lee. "Even with $4 corn, we're talking about a $32 return per inch of water that we apply. That's a no-brainer since it doesn't cost us nearly that much. Water is literally an investment," he says.
The basic strategy for corn production is "what you do, when you do it, and how you do it," he continues.
"It's all about understanding growth and development, and then balancing the costs of production. We can throw the kitchen sink at it, but is it profitable? One of the things about irrigation is learning how to use this tool – and it goes along with learning to use the planter, the plow, the sprayer and the combine. It's just one of several tools, but it is all about reducing plant stress."
Growers should understand the stages of a corn crop, he says, and the water use requirements at each stage. "By the time you get a plant that's 13 to 14 inches tall, you're at a V6 stage, and that crop is no longer making leaves. It's done, and now you're making a tassel and the ear."
Lee sees a few common irrigation mistakes each year, including allowing the plants to stress. "How many times have you heard this before – 'I want the crop to stress a little bit, and I want those roots to go down and find that water.' But it doesn't find water, it grows through water. It doesn't grow through dry dirt."
The V6 stage is determined by looking at the upper most leaf that has a visible collar.
"This light green collar is just like the collar on a shirt – the neck or stalk of the plant is nested within it. If you see this collar, that's where your stages begin, from there up. All of these leaves and cells are expanding, and we want to think about that timeline. Because at this point, you have a tassel, an ear and kernels are growing until you get to the silking stage."


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|To All Employees,
The IT Access Administration Office would like to announce some changes to the online access request form (http://www.utpa.edu/accessrequest).
Notification reminders for approvals at any level (ex. supervisor, resource owner, etc.) will be sent out at 12:30 am until the request is approved.
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Character matters.
And it doesn't hurt if you've got heart.
The Saginaw Spirit displayed both Tuesday night in beating the Guelph Storm 7-6 in double-overtime before a crowd of 4,439 in TheDow Event Center's Wendler Arena.
Defenseman T.J. Brodie scored the game-winner at 5:40 of the second OT on a low shot from the blue line with Saginaw on a power play.
The victory gives Saginaw a 3-0 lead in a best-of-seven Western Conference quarterfinal series. The Spirit can move on to the second round for the first time in the seven-year history of the franchise with a win Thursday night at the Sleeman Centre in Guelph.
"I thought we played a pretty good game up 2-0, 4-2, 5-3 and we kept digging down deep," Saginaw head coach Todd Watson said. "Guelph kept digging down deep. These two teams are evenly matched. Two overtime games; you can't say it's not evenly matched.
"A big night by a lot of guys. We battled and we were fortunate to get that last goal."
Saginaw is on the verge of playing in a conference semifinal because they refused to yield Tuesday night after giving up the 2-0, 4-2 and 5-3 leads. The Spirit even kept battling after they let a 6-5 advantage slip away.
"It's really easy to pack it in when you have a two-goal lead multiple times and give it up," Saginaw center Tyler Murovich said. "It's real easy to let the wind out of the sails in the room, pack it in and we didn't do that.
"Guys stuck together and played hard and it showed."
That's character, a trait his team has displayed throughout the season, Watson said.
Eddie Pasquale was in net again for Saginaw and he showed some of that grit when he stopped all 11 shots he faced in both overtimes after struggling a little in regulation.
Murovich and Jack Combs drew the assists on the game-winner, just moments after Murovich failed to slide the puck into a wide open net. The goal judge even turned on the red light in anticipation of Murovich ending the game.
"Boy, am I ever glad T.J. scored, that's for sure," Murovich said with a laugh.
So while officially Murovich and Combs assisted on the game-winner, Spirit goalie coach Randy Wilson also drew an assist.
"Yeah, just before I went on the ice for the second overtime Randy told me to shoot low stick side and I'd score," Brodie said. "That's just what I did."
Combs did a lot of shooting himself, finding the back of the Storm net twice and he added two assists for a four-point night. The 20-year-old center has six goals in the series.
"I really haven't changed anything other than I've brought back out the white shoes," Combs said with a smile.
Comb broke out the white bucks late in the regular season when he struggled through a long goal-less drought. But wearing the shoes, he scored in three straight games.
"Our line is really playing well," Combs said. "It's a tribute to my linemates, (Chris) Chappell and (Kyle) Bochek. We're all over it right now. We feel like we're playing really good right now."
Chappell scored once and added two assists in the double-OT win, while Bochek contributed a goal an assist.
Also scoring for the Spirit was Joe Pleckaitis, he was the back end of two goals in 11-seconds in the first period that give their team a 2-0 lead.
But by the end of the opening 20 minutes the score was deadlocked at 2-2.
Combs opened the second period with two goals in three minutes, making it 4-2. But the Storm sliced the advantage to 4-3 heading into the third period.
The Spirit increased their led to two goals again at 4:24 of the third period on a power-play goal from Murovich.
Guelph's Peter Holland and Matt Kennedy responded with goals to make it 5-5.
Chappell put Saginaw out in front again, this time at 11:26 of the third, but Holland completed a hat trick at 15:26, sending the game into overtime.
Watson will make it clear to his team at practice today they have accomplished nothing, yet, despite the 3-0 lead.
"I've seen the Soo was up 3-0 on Windsor (several years ago) and Windsor won that series 4-3," Watson said. "And last year in the OHL championship series, Kitchener, who was an outstanding team, close to what Windsor is this year, was up 3-0 on Belleville.
"But Belleville came back to tie it 3-3 (before Kitchener won the series). So (this season) is far from over."
Mark Constantine is a sports writer for The Saginaw News. You may reach him by calling 776-9769 or at firstname.lastname@example.com


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The hockey-mad Web site "Kukla's Corner" recently asked my about my impression of Darren McCarty's month-long stint with the Grand Rapids Griffins.
Click here to read the short question-and-answer session about McCarty
By the way, if you're looking for a comprehensive site with plenty of Detroit Red Wings coverage (or, shoot, any hockey tidbits), this definitely is one to check out.
E-mail Michael Zuidema: email@example.com


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What do you think dooes each idioms mean?
1. get your feet under the table
It only took him a week to get his feet under the table, then he started to make changes.
2. burn the candle at both ends
He's been burning the candle at both ends to finish this project.
3. put pen to paper
She finally put pen to paper and wrote the letter.
4. go the extra mile
She's a hard worker and always goes the extra mile.
5. pull your weight
He's a good team worker and always pulls his weight.
6. put your feet up
At last that's over - now I can put my feet up for a while.
7. take on
They're taking on more than 500 people at the canning factory.
8. get the boot
She got the boot for being lazy.
9. give someone the sack
He was given the sack for stealing.
10. give someone their marching orders
After the argument, he was given his marching orders.
Proverb of the Day:
"A good beginning makes a good end."
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