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a difficult transition. For example, study strategies that may have worked well in high school may no longer ... work in college level courses. Students may find themselves struggling. The College Success Counselor ... provides one-on-one and in-class workshops to assist students with: Note Taking Strategies Study Strategies ...
Check Cattle for Lice in Late Winter/Early Spring
economic impact. One factor that can reduce the negative effect of lice is a high energy diet. ... heavy lice infestations are most often seen during winter months. There are two type of lice that may ... infect cattle: sucking lice and biting lice. It is possible to have both types of lice on any one ...
Mid-Ohio Small Farm Conference
may be just what you need. Besides the opportunity to learn from presenters about specific small farm ... small farm owners. The trade show includes vendors and exhibits that may be the answer to questions you ... have or that may provide resources/products that match your small farm enterprise needs. The ...
Module 3: Dairy and Beef Cattle
M odule 3: Dairy and Beef Cattle In this module we will briefly discuss the economic importance of ... the cattle industry, cattle industry risk management, the main cattle breeds found in Ohio, equipment ... receipt of your payment by Ohio State University. That message will also provide instructions on how ...
Market Connection With OSUE
produce. OSUE will staff a table once a month from May through October 2020 at either the downtown market on ... to seeing you on May 30th. ...
You Can Feed Student Success!
the Buck-I-EAT development fund (315953). The Buck-I-Eat program was inspired by members of the Ohio ... The Buck-I-Eat food pantry is maintained by generous donations from the Ohio State ATI community. For ... more information contact Ruth Montz email@example.com, Co-Advisor, Ohio State ATI Collegiate FFA ...
Introduction to Agriculture
Welcome In this series, you will begin by learning about the agriculture industry in Ohio and ... beef cattle, etc. Who Is It For This professional development series was created for people working in ... will earn you a certificate of completion to document your professional development. Once registered, ...
Women in Agriculture Conference
Communication; Home & Family; and Special Interest. As always, Ohio FFA state officers will be teaching one ... The 7 th Annual East Ohio Women in Agriculture Conference will be THURSDAY, March 19 from 9:00 am ... Massillon, OH 44646. This year's program will feature 18 break-out sessions presented by OSU Extension ...
Random Acts of Kindness
They show several studies that kindness is indeed contagious. When something nice is done for one ... outside of that circle like a new student at school, a new neighbor or a community service group. It may ... distant from us, like members of a sports team if they choose to quit? Make sure children are friendly ...
Mobile Design Lab on campus
our prepared workshops or partner with a Digital Flagship team member to create one specific to your ... possible for all Ohio State students, staff, and faculty to build comprehensive digital skills through ... coding education, app development experts, community projects and state of the art technology available ...


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Pro Musica, Pro Dramatis and Pro Artis Detailed Information
Who is eligible for a Performing and Visual Arts Scholarship?
Any new student accepted at Augustana University by February 1, 2020, is eligible to apply for a music, theatre and/or art scholarship.
Scholarship Amounts and Criteria for Maintaining Scholarship
Scholarships are annual allocations and automatically renewable. Criteria for maintaining a scholarship varies from department and is generally a commitment to participate in departmental ensembles, performances or activities. All students must maintain a 2.5 grade point average. Criteria and scholarship amounts as listed here are subject to change.
Steps to applying for a Performing and Visual Arts Scholarship:
- Be admitted to Augustana University by February 1, 2020.
- Submit the Performing and Visual Art Scholarship Application Form. Priority will be given to those students who apply by February 1, 2020. Part of the online application includes an area where the applicant can select and notify the person who will submit their letter of recommendation. The letter of recommendation should be submitted from a teacher representing each scholarship area for which a student is applying, i.e., vocal, instrumental, keyboard, strings, theatre, art.
- You will be notified as to the time and place of your audition or portfolio review.
- Audition (music and theatre) or bring your portfolio for review (theatre design or art only) on one of these dates. All are held on Augustana campus, except where noted. If you are unable to attend any of these dates, you may submit your portfolio/audition materials online through the scholarship application:
- Sunday, November 24
- Monday, January 20 (No theatre auditions available)
- Friday, February 7 (Visual Art only)
- Sunday, February 16
- Sunday, February 23
Pro Musica Scholarship Information Only
Band Audition Informational Video
Choir Audition Informational Video
Amounts and Criteria for Maintaining Scholarships
- Mozart Award: $5,000 annually/$20,000 over 4 years
- Bach Award: $3,000 annually/$12,000 over 4 years
- Beethoven Award: $2,000 annually/$8,000 over 4 years
- Brahms Award: $1,000 annually/$4,000 over 4 years
Vocalists and instrumentalists (not keyboard students) must participate in a major ensemble as defined by the university. Ensemble auditions are held in the fall before classes begin. Scholarship awards greater than $2,000 require that the recipient register for applied lessons during the first four semesters of the award which are at an additional cost. View fees for applied lessons here.
Keyboard scholars are required to take lessons every semester for the duration of their scholarship. The cost of these lessons will be supported by scholarship funding for all four years; the lessons will be graded A-F in years one and two; and graded S/U in year three and four. Scholarships over $2,000 may require up to four semesters of accompanying or chamber music when appropriate or available. Scholarship awards greater than $2,000 require that the recipient register for applied lessons during the first four semesters of the award which are at an additional cost. View fees for applied lessons here.
Pro Musica Audition Selection Recommendation
Instrumentalists perform one or two selections. Vocalists sing two selections of contrasting styles. One or both of the pieces may be in a foreign language, but is not required. Selections should demonstrate technique and musicality. The level should be suitable for solo/ensemble contests. The time should be approximately 3-6 minutes.
The university will provide an accompanist for vocal auditions only. The piano score(s) must arrive at least 2 weeks prior to the audition date. Instrumental auditions may be performed without accompaniment. Please indicate on the audition form if you wish to have an accompanist provided (vocal auditions only).
Submissions for those unable to attend
If you are unable to audition in person, you may submit recordings of your audition in the media area of the online application form. Accepted formats for audio include .aac, .aif, .aiff, .iff, .fla, .m4a, .mpa, .mp3, .ra, .wav, .wma. Accepted formats for video include .avi, .flv, .m1v, .m2v, .m4v, .mkv, .mov, .mpeg, .mpg, .mp4, .webm, .wmv. You may also link directly to any media you have uploaded to locations such as Vimeo, YouTube, SoundCloud and Sketchfab. Please submit your piece(s) by March 1, 2020.
Pro Artis Information Only
Amounts and Criteria for Maintaining Scholarships
Scholarships ranging up to $2000 will be awarded by the Art Department. Art scholars must assist in the Eide/Dalrymple Gallery for 16 hours each semester. Assigned duties may include assisting to hang and take down gallery exhibits, monitoring the gallery during open hours, assisting with gallery receptions, working on preservation, framing and cataloguing of the permanent collection.
Pro Artis Portfolio Review Recommendations
Students should bring 5-10 works of art in any media representing at least two different media. Works do not need to be framed and are simpler to transport if they are not framed. Students should also bring a typed "Artist Statement" of one or two pages which will be read during an interview with faculty where the student's work will be presented. The artist statement will be submitted to art faculty after the interview. The statement can address some of the following:
- Description of some of the successes and struggles that you have experienced in creating either your artwork in general or a specific project.
- What inspires you as an artist?
- What does creating art mean to you?
- Do you have a favorite medium? If so, what is it about that medium that attracts you?
Portfolio submissions
Students who cannot come to campus to have their portfolio reviewed should submit their portfolio in the media area of the online application form. The portfolio should include digital pictures of 5-10 works of art (jpeg, gif, tiff, bmp, png), a list of the submitted artworks including title, dimensions, medium, year in school that the work was created (e.g., 2019 as a junior), class that the work was created for and an artist statement of at least 300 words addressing the questions listed above. Please submit the portfolio by March 1, 2020.
Pro Dramatis Information Only
Pro Dramatis Audition Informational Video
Amounts and Criteria for Maintaining Scholarships
Scholars and majors form the core of the Augustana Theatre Company. Scholarships ranging up to $2,000 will be awarded. Theatre scholars must participate in company call one evening per week, assist in the scene and costume shops for four hours each week or hold specific leadership roles to fulfill their scholarship obligations. These roles may include but are not limited to the following: scenic, lighting, sound or costume designer; company manager, shop foreman, master electrician, front of house director.
Pro Dramatis Audition Selection or Portfolio Recommendation
Auditions should consist of two monologues of two minutes or less each of differing styles and tone. Portfolio should consist of photographs of completed designs.
Audition/portfolio submissions
- If you are submitting a portfolio, please include photos of finished designs for sets, lights and/or costumes (jpeg, gif, tiff, bmp, png), and include an explanation of photos that include show name, design area and year in school that the design was done (e.g., 2019 as a junior).
- If you are submitting an audition, accepted formats for audio include .mp3, .wma, .ogg and .flac. Accepted formats for video include .m4v, .mov, .mp4, .wmv, .flv, .asf, .mpeg, .mpg, and .mkv. You may also link directly to any media you have uploaded to Vimeo, YouTube, SoundCloud and Sketchfab.

subset: commoncrawl


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Icon, 2007 - Atomic theory - 206 pages
All things are made of atoms, little particles that move around in perpetual motion, attracting each other when they are a little distance apart but repelling upon being squeezed into one another. This is the first popular account of the fascinating story of the atom. No one ever expected the atom to be as bizarre, as capricious, and as weird as it turned out to be. Its story is one riddled with jealousy, rivalry, missed opportunities and moments of genius. John Dalton gave us the first picture of the atom in the early 1800s. Almost 100 years later came one of the most important experiments in scientific history, by the young misfit New Zealander, Ernest Rutherford. He showed the atom consisted mostly of space, and in doing so turned 200 years of classical physics on its head. It was a brilliant Dane, Neils Bohr, who made the next great leap - into the incredible world of quantum theory. Yet, he and a handful of other revolutionary young scientists weren't prepared for the shocks Nature had up her sleeve. Mind-bending discoveries about the atom were destined to upset everything we thought we knew about reality. Even today as we peer deeper and deeper into the atom, it throws back as many questions at us as answers.
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From botany to the atom
The reluctant revolutionary
Fifteeninch shells
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Samantha is doing her homework but she is quite distracted by the horny fantasies ging through her mind. As soon as her teacher isn't watching she is masturbating with her ballpoint. But then the teacher wants to borrow it...
Watch the whole story!
Old farts luring teens into sex!
Horny old men on the hunt for some nasty teenage pussy!
Watch the full set!
Cute teen girls who're tricked into sex with horny old seniors!
18 U.S.C. Section 2257 Compliance Notice - http://www.imco.nl/2257/


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The first Winx game for the PSP® systemcombines magic, fashion and action to create a must have game for girls of all ages.
Welcome to the magical world of Winx Club where players can explore a wide range of new characters, interactive environments and fun mini games that incorporates the fashion, friendships, and magic of the Winx Club world. Players will be able to enjoy a simple, social and fun game experience that is designed specifically for girls 6-11. The storyline based on the second season of the hit animated series. Fast paced mini-games for each playable character. Win items to customize your character and dorm room.


text: Psychology is the scientific study of mental processes and behavior. It is a broad field that encompasses many interests. Psychologists develop knowledge and techniques that benefit all disciplines. Many of our students integrate their work in psychology with their other interests. Psychology students learn how to collect, interpret, and present data about human subjects and understand social relationships. Graduate students in our counseling program and dual degree law programs engage in coursework and experiential training designed to prepare them for rewarding careers in their respective professions.


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5/20/2009 Senator Montgomery News Conference "Anti Shackling Bill" (S.1290- A/A.3373-A)
Albany, NY (May 20, 2009): Human rights advocates and champions of criminal justice reform joined today with sponsors of the "Anti Shackling Bill" (S.1290- A/A.3373-A) to hail the Senate and Assembly's passage of legislation that prohibits the inhumane practice of shackling pregnant inmates who are in labor. The announcement was made at the State Capitol in Albany, New York. The "Anti-Shackling Bill" is sponsored by Senator Velmanette Montgomery (D-Brooklyn) and Assemblyman Nick Perry (D-Brooklyn).


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I know this may seem like a Halloween lesson, it's actually another face style tutorial that will show you "how to draw a Grim Reaper face", step by step. The simple style and design concept is going to make this reaper a blast to recreate. You can color in the eyes as I did with a nice hazy glow, or you can keep things simple. One thing's for sure, you will definitely like drawing a Grim Reaper face. That's all I have for you all so I hope you enjoyed today's lessons. I will be back tomorrow with more drawing fun.
DragoArt members upload artwork and drawing tutorials! They are also allowed to leave comments on tutorials, profiles, etc. Many more features, as well; it's way better than just being a boring guest! Register Now!


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Read an interview with Linda Glaser, author of Hannah's Way (Sydney Taylor Book Award in the Younger Readers Category) at This Messy Life! A highlight: "This is a story about staying true to one's traditions but still wanting to "belong." It's also a story about ordinary children who, through a simple act of kindness, become heroes. I hope that with the help of the Sydney Taylor Award, Hannah's Way will reach many more kids and will do its small part to encourage tolerance, acceptance, and kindness."
Read an interview with Adam Gustavson, illustrator of Hannah's Way (Sydney Taylor Book Award in the Younger Readers Category) at Here in HP!
A highlight: "I've always drawn; my mother was an artist when I was
growing up, and my brothers and I drew like most other kids would play
ball. It was a big part of how we played together. My father, an
engineer, used to come home with art supplies he'd picked up for us on
his way home from work. I grew up in the only household for miles and
miles where a crisis consisted of my mother trying to find out just who
took her kneaded eraser."
Randomly Reading!
A highlight: "Young readers have much longer lives ahead of them. I
want them to be inspired by this man and by his character and actions.
I want kids to know that they too can make a positive difference in the
world. I want them to find their own heroes. And I want readers to
remember Raoul Wallenberg and to carry his story into their own futures.
We are all storytellers - kids will remember a great story and I hope
they will tell others and use its power for good in their own lives."
Read an interview with Deborah Heiligman, author of Intentions (Sydney Taylor Book Award in the Teen Readers Category) at The Fourth Musketeer!
A highlight: "I wanted to capture that moment in a teen's life when she
realizes that someone she adores and even idolizes is flawed. That
happened to me in a pretty spectacular way in my community growing up
(though not quite as spectacularly as in the book!) and it was a truly
painful time. That moment informs who you become I think--because how
you deal with it can shape the rest of your life."
A Podcast About Jewish Kidlit (Mostly)
Listen with Apple Podcasts, Spotify, Google Play, Google Podcasts, Stitcher, or TuneIn, or anywhere else using our RSS Feed.
Tuesday, February 12, 2013
2013 STBA Blog Tour: Day 2
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Address: 103.5 N. Main St. Breckenridge, CO 80424
Phone: (970) 547-9998
Reservations: Operates on a first come first served basis.
Website: aspenthai.net/Breckenridge-thai-food (jump directly to the menu here)
Bangkok Happy Bowl Thai Bistro and Sushi Bar…
Owned and operated by an award-winning husband and wife team, Bangkok Happy Bowl offers fresh and delicious Thai food, sushi, sashimi, noodles, and more, right in the heart of Breckenridge. Enjoy a meal in the beautifully renovated restaurant, full bar, or rooftop patio (weather permitting). Bangkok Happy Bowl offers daily happy hour, Sushi Sundays, and lunch specials. Scroll down for details.
Local's Tip: Check out BHB weekdays for complete lunch specials at killer prices, and Sake Bombs are always on the menu! Feeling extra hungry? Try a "Sushi Boat" for the freshest selection of sushi in Breck.
Bangkok Happy Bowl's Upcoming Specials and Events:
$5 House Sake, $3-4 Beers, $1 Off Drinks, $8 Classic Sushi Rolls and BOGO AppsFriday, September 13, 2019 from 04:00 pm to 06:00 pm
Event Details
Breckenridge, Colorado, United States, 80424
Enjoy Happy Hour every day from 4-6pm at Bangkok Happy Bowl. Specials include:
-$1 Off Drafts, including Sapporo, Dale's Pale Ale, Fat Tire, Blue Moon and Ranger IPA (Coors Light is $3 and all others are typically $4 each)
-$1 Off Well Drinks
-$1 Off Glasses of House Wine
-Featured Cocktail of the Day
-$5 House Sake
-$8 Classic Sushi Rolls, including shrimp tempura, spicy ahi, spicy salmon, spider rolls and more
-2 For 1 Appetizers, including egg rolls, edamame, gyoza and more
*Tip - Bangkok Happy Bowl also offers a rooftop deck (weather permitting)!
Cost & Tickets
Bangkok Happy Bowl
Organizer website
Bangkok Happy Bowl
Breckenridge, Colorado, United States


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So in a few short months I am going to be moving into my tiny house and there are three things that I am really having a hard time trying to figure out how I'm going to handle getting into my tiny house. They are things that I use very rarely, but there isn't a good option to not having them. I thought I'd air my metaphorical "dirty laundry" out for everyone to see, and just maybe I could get some ideas from you all.
So the three things things that I have been having a hard time paring down on are
- Tools
- Camping equipment
- Reference books and materials for my job
Going through this list I obviously still need my tools for building my house and I have several smaller projects to do after the house, so as of right now I use them every week, but what about after? I have quite a few power tools that I'd really like to keep, but there is really no place in a tiny house for all of them.
I wrote about this a little bit in this post and I have been thinking I'd like to build a tiny house office in the near future. Basically the tiny house office will be for me to shift my job to a work from home job 100% of the time, I think it is important to have a separate space to work in so you can leave it behind when you need to. My tools take up about 30ish cubic feet right now, so in the grand scheme of things not a whole lot, but too much to pack into the house; they are something that I do want to keep.
Camping/backpacking is one of my hobbies that I have have done since I was 12, I have literally backpacked a few thousand miles with a 40lb pack on my back. I love the views, the time away from it all, and the time spent with friends. The gear for this hobby is quite specialized and pretty expensive. As I have curated my "perfect system" over the years I have gotten down my weekend pack down to an impressive 24 lbs including my water! The trouble with camping things like tents and sleeping bags, you have to store them loosely to not damage them. Loosely meaning it takes up a lot of space, not ideal for a tiny house.
I've thought about selling it and then renting it when I need to, but honestly the idea of renting a sleeping bag that others have hiked all day and then slept in is not something I could handle… pretty gross. Besides my gear is markedly better than what they have for rentals around here.
Finally I have quite a few materials, books and other things that I need to do my job. I am a very big proponent of digitizing things, minimizing, streamlining, but in the end, you need the tools to do your job. This is an interesting difference between me and a lot of other tiny house people. To add to the difficulty I am doing two jobs right now, the one that I'm doing and then the one I want to be doing full time. While there are quite a few that live and work from a tiny house, their jobs seem to lend themselves to it. My current job doesn't so this is in part why I am considering building my tiny house office.
So that is my conundrum at this point, I've been wrestling with this for a while and haven't really come up with a good answer. Thoughts?


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Got Leftover Bagels? Turn Them Into French Toast
I still remember walking past a sign in England advertising a morning special of "bacon on a bagel of your choice: 99p" and laughing. I wasn't sure if that was the most tref unkosher food I'd ever seen—or the least.
My companion didn't immediately understand what was so funny. During such moments, as an East Coast resident of the United States, I truly understood Lenny Bruce's definition of Jewishness:
To me, if you live in New York or any other big city, you are Jewish...It doesn't matter even if you're Catholic; if you live in New York you're Jewish. If you live in Butte, Montana, you are going to be goyish if you're Jewish.
I wasn't raised Jewish, and my great-grandfather's faith only gives me the most tenuous of genetic links to the tribe, but that's never stopped me from preferring challah to champagne as New Year's food, and latkes to eggnog in the wintertime.
To prove Bruce's thesis, a friend of mine (raised Catholic) moved away from New Jersey to Ohio after her husband's job was transferred to the Midwest. I reconnected with her on Facebook (of course) and at least every other week I read a status update counting the days 'till she can visit her mother in New Jersey, reconnect with old friends, and reconnect with real bagels and pizza. Other mothers in Ohio send their children to bed telling them that LeBron James is not a role model, my friend Jennifer tells her children that the bread products they get at their friend's houses are "puffy roles with holes in the middle of them," not real bagels. Real bagels and pizza are where grandma lives. (Regarding pizza, the words "ketchup" and "cardboard" have been used).
Despite the ubiquity of bagels in delis and supermarket freezer sections across the country, there aren't that many "second life bagel" recipes. Challah is often used for French Toast and bread pudding—bagels, not so much. Yet so many places are littered with spare bagels, since the temptation is always to buy a dozen, even if only six people work at the office and two of them are on Atkins.
So what about using a bagel to make French toast? When I first began living alone, slicing a leftover bagel into halves or thirds, soaking the slices in an egg and milk batter until softened and frying them up seemed natural. Served with honey, maple syrup, or even stuffed with cream cheese and fruit, it's the perfect second-life-of-bread kind of treat, especially if you're not terribly fond of overly eggy French toast. As a tot, I was frustrated about not being able to chew a bagel with my baby teeth, so French toast bagels are an ideal way for even the tiniest of mouths to enjoy this bread icon.
And if you can only get real bagels every so often—whether for you that means bagels from your favorite establishment in Maine, Montreal, Cleveland, New York, or New Jersey—you can take home a very large bagful and transform them, for many weeks afterward.
I can hear Linda Richmond in my head now..."This French toast is neither French nor toasted! Discuss!"
Note: Very stale bagels might require a longer marinade in the milk and egg mixture.
All products linked here have been independently selected by our editors. We may earn a commission on purchases, as described in our affiliate policy.


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Say I have an arbitrary RLE Sequence. (For those who don't know, RLE compresses an array like [4 4 4 4 4 6 6 1 1] into [5 4 2 6 2 1]. First comes the number of a particular integer in a run, then the number itself.)
How can I determine an algorithm to set a value at a given index without decompressing the whole thing? For example, if you do set(0,1) the RLE would become [1 1 4 4 2 6 2 1]. (In set, the first value is the index, the second is the value)
I'm trying to find an efficient way to do this, right now I can just think of methods that have WAY too many if statements to be considered clean.


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Feel - cord bracelet
Sterling Silver Cord Earring, Rings, Bracelets, Pendants & Fine Jewelry to Spread Love
Discover the beautiful world of fabulous, outstanding and excellent sterling silver cord jewelry inspired by the Russian soul. Amorem Jewelry is a famous brand supplying lovely sterling silver cord bracelets, cord charm bracelets, pure silver above knuckle - mid finger and all finger rings, pretty charms, stylish cord pendants, sterling silver pendants for women, different symbol and inspired quote cord bracelets, infinity symbol charm bracelets and popular unique stylish sterling silver earrings for women at one place. Celebrate love and romance with our stunning collection of sterling silver rings. Discover the inspirational jewelry that carries deeper meaning and divine thought. Through our fine jewelry we help people express their feelings.
We share love across the world through all our sterling silver cord jewelry products that made with acute care. Spread love with our sparkling sterling silver jewelry, open your heart and let love shine through you.


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Services on Demand
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Related links
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Anales de la Asociación Química Argentina
Print version ISSN 0365-0375
An. Asoc. Quím. Argent. vol.94 no.1-3 Buenos Aires Jan./July 2006
Theoretical study of the outer valence photoelectron spectra of methyl nitrite and fluoromethyl nitrite
1Estrada, M. R.;1 Zamarbide, G. N. ;2Sánchez-Marín,*J.
1 Universidad Nacional de San Luis. Chacabuco y Pedernera 5700, San Luis, Argentina
2 Universitat de València, Institut de Ciència Molecular, Apartado de Correos 22085. Valencia E-46071. Spain
FAX: +34 96 354 3274; E-Mail: email@example.com
Received March 31st, 2006. In final form May 2nd, 2006
Dedicated to Prof. Imre G. Csizmadia on the occasion of his 75th birthday
The effect of the syn-anti conformational isomerism and fluorination of methyl nitrite on the ultraviolet photoelectron spectra of methyl nitrite is predicted on the basis of Outer Valence Green Function calculations using the 6-311++G** basis set. The conformational space of methyl nitrite and its single, di- and tri-fluoromethyl derivatives have been explored with MP2 and B3LYP-DFT approaches. Only the fluoro-methyl nitrite shows minima with geometries compatible with bound systems, therefore the OVGF study has been limited to methyl nitrite and fluoro-methyl nitrite. A procedure has been devised to represent simulated spectra starting from the OVGF data and the experimental UPS spectrum taken from the literature. The He I experimental spectrum has been assigned at the OVGF level and the simulated spectra are discussed. It is predicted that the syn-anti conformational isomerism will affect less the spectrum of the fluorinated system than that of the methyl nitrite. The effects of fluorination will be larger for the second peak than for the first. Fluorination brings about changes of the general shape (e.g., peak shifts, changes in gap widths, positions, etc.) of the low ionization energies of the spectrum.
Se predice el efecto del isomerismo conformacional syn-anti y de la fluoración del nitrito de metilo sobre el espectro fotoelectrónico ultravioleta del nitrito de metilo a partir de cálculos con el método de funciones de Green para la valencia externa (OVGF) usando el conjunto de base 6-311++G**. El espacio conformacional del nitrito de metilo y sus derivados uni, di y tri-sustituidos se ha explorado con las aproximaciones MP2 y B3LYP-DFT. Unicamente el nitrito de fluormetilo muestra mínimos que tienen geometrías compatibles con sistemas enlazados. Por esa razón el estudio OVGF se ha limitado al nitrito de metilo y a su derivado monofluorado. Se ha puesto a punto un procedimiento para representar los espectros simulados a partir de los datos proporcionados por el cálculo OVGF y el espectro experimental del nitrito de metilo tomado de la literatura. El espectro He I experimental ha sido asignado de acuerdo con los resultados OVGF, y esto ha permitido discutir los espectros simulados a partir de los cálculos. Se predice que el isomerismo conformacional syn-anti afectará menos al espectro del derivado fluorado que al del nitrito de metilo. El efecto de la substitución por F será mayor en el segundo pico del espectro que en el primero. Los cambios en el espectro producidos por la fluoración serán fácilmente reconocibles por los notables cambios en la forma general del espectro (desplazamiento de los picos, cambios en las separaciones entre bandas, etc.) en la región de bajas energías de ionización.
The reactivity of Alkyl nitrites, and notably that of the first member of the series, methyl nitrite (MeONO), has deserved interest because these compounds are sources of the methoxy and NO radicals [1,2,3]. The properties of methyl nitrite [4] and other alkyl nitrites [5] as nitrosation agent have been also recently studied. On the other hand, the cis-trans (more properly, syn-anti) unimolecular isomerization with respect to the O-N single bond of methyl nitrite (see scheme 1) has been the subject of accurate theoretical and experimental studies because in this case a low energy barrier occurs, along with a low density of vibrational states [6].
The relative stability of syn and anti conformers in alkyl nitrites has also been studied in detail [7,8]. In particular, for methyl nitrite, the syn conformer appears as the most stable for a wide range of temperatures [7], while for ethyl and higher alkyl nitrites, the situation is more involved [8,9] and stereoelectronic effects, dynamic chirality and other conformational effects related to the cis-trans behaviour with respect to the C-O bond need to be considered.
Flourinated alkyl nitrites seem to have been little studied and references to fluorinated alkyl nitrites are hard to find. Fluorine is a strong electronegative substituent that increases the electron density in its proximity. It is well known that CF3- is a prototype of meta-orienting with deactivation substituent in aromatic substitutions that leads to 100% meta-oriented nitration in fluoromethyl-benzene [10]. On the other hand, the nitrooxymethane group is very reactive as indicated above. One can think of fluorinated alkyl nitrites as reactive and unstable. In fact, as it will be shown in the results section, stability difficulties related to fluorination of the methyl nitrite can be expected. Hence, the theoretical study of the electronic properties of fluorinated alkyl nitrites appears to be in order as experimental studies will face difficulties. It can be advanced here that, as it will be shown in the results section, only the singly fluorinated methyl nitrite is found to show minima with common geometrical properties.
This preliminary study is focussed on the one-electron energies that are commonly measured by photoelectron spectroscopy and related techniques. At this point we can take benefit of the experimental UPS spectrum of methyl-nitrite reported by D. Wang et al. [11]. Ultraviolet photoelectron spectroscopy (UPS) is an appealing technique to theoreticians as it can be interpreted on the basis of the MO theory provided by Koopmans theorem [12]. However, it is well known that the correlation and orbital relaxation effects not included in the one-electron Hartree-Fock model are needed for a proper accounting of the ionization energies measured through the UPS techniques [13,14]. This is generally true even for those cases where the ionization process can be properly described as a single-particle single-step process. The outer valence Green function (OVGF) method [15,16,17,18] provides a convenient way for taking into account correlation and relaxation effects in a direct (i.e., not as a difference of energies) calculation of ionization potentials (IP), conserving the description of the ionization process as related to a single MO.
This work aims to calculate the UPS spectra of methyl nitrite and fluoro-methyl nitrite by means of the OVGF method in order to evaluate the influence of the syn-anti conformations in the UPS spectra and the influence of F substitution in the UPS spectrum of methyl nitrite. Another goal of this work is to use the experimental UPS spectrum of methyl nitrite as a pattern against which the calculated data can be compared. In order to get realistic simulated spectra the calculation was started from the available experimental data of the UPS spectrum of methyl nitrite [11]. The procedure is described in the next section.
Methods and Calculation Conditions.
The vertical one-electron ionization potentials, IP, have been calculated with the SCF and the OVGF methods. Geometry optimizations have been performed with the DFT approach with the B3LYP functional (Becke hybrid three-parameter nonlocal exchange functional combined with the Lee-Yang-Parr dynamic correlation one) [19,20]. As shown below, the DFT results reveal that, for the fluorinated methyl nitrites, methods to calculate explicitly the dynamic correlation effects are required. As a consequence, the optimized MP2 geometries have been preferred to the DFT in the OVGF calculations.
All the calculations reported in this work have been obtained with the valence triple zeta, polarized and singly augmented basis set usually denoted as 6-311++G(d,p). This basis set provides a convenient compromise between the desired accuracy (suitable for the purposes of the present work) and the required computational effort, both for geometry exploration and OVGF ionization energies.
Previous calculations on the conformational space of ethyl and methyl nitrites can be found in the literature [6,8,9]. Taking the existing works on alkyl nitrites as a guide, the set of expected conformers of methyl nitrite and fluorine substituted methyl nitrite have been optimized for the conditions of the present work. Such optimization of geometries has been attempted using the B3LYP density functional. The non-substituted and single-fluorinated molecules have led to well conditioned and geometrically consistent minima at the B3LYP level. However, doubly and fully substituted methyl nitrites have led to minima that show abnormally long single bond O-N length (see the results section for further details).
At long bond distances, the van der Waals dispersion effects between the two resulting molecular fragments (the [NO.]-like fragment and the [O-CF3.]-like fragment) can be critical in order to describe properly the molecular system. Unfortunatelly, the DFT models cannot deal in most cases with inter-molecular or inter-fragment dispersion effects [21]. These effects require a detailed calculation of simultaneous local single excitations that can be accounted for, e.g., by MP [22] approaches of second order (at least). Hence, all the geometrical structures in the present work have been optimized looking for MP2 energy minima. It is clear that in those cases where the minima show conventional bond distances and angles, the B3LYP geometry and energies should be considered better. However, in the present case a consistent set of energies and geometries can be more likely obtained with the MP2 approach in order to deal with inter-fragment dispersion effects. All the minima have been verified analytically to have all positive hessian eigenvalues.
As it was indicated above, the outer valence IP's corresponding to each structure have been calculated with the OVGF approach [15,16,17]. The OVGF method can be described as a third-order (with extensions in which some higher order terms are taken into account) perturbative-type single particle Green's function method [18]. These kind of methods have as zero order the Koopmans' ionization potentials, so that a one to one correspondence can be established between each OVGF pole and just one MO from which the electron is removed.
The UPS spectra have been simulated by means of gaussian curves weighted by the OVGF pole strength squares and centered at the IP values. The FWHM was 0.5 eV. throughout. This FWHM value accounts for the non-resolved vibrational widening of the low IP bands in ordinary low resolution spectra. This simple procedure cannot reproduce some effects, such as the spread of intensities of each one-electron ionization in a number of multi-electron processes (e.g. shake-up lines), that attenuate the intensities and crowd the lines at high IP values. In order to reproduce the experimental attenuation of the spectra of alkyl-nitrites as reported by Wang et al. [11], the whole calculated spectrum has been dumped by a single gaussian centered at the onset of the spectrum. The exponent of this dumping gaussian factor (-0.02) was chosen to simulate the attenuation of the low resolution experimental spectrum of methyl nitrite [11]. This experimental spectrum is conveniently simulated by centering each band at the experimental band maximum reported in ref. [11], and giving the same weight (0.8) and same FWHM (0.5 eV) to each gaussian curve. The same dumping gaussian factor has then been used in all the calculated spectra. However, in the case of calculated spectra, the individual contribution of each band has been weighted by the respective squared pole strength provided by the OVGF calculation. All the MP2, DFT and OVGF calculations reported in this work have been performed with the gaussian 03 program system [23].
Table 1 shows the energies of the minima at the SCF, MP2 and B3LYP-DFT levels. Only the energy values of the most stable conformations for each syn and anti conformer are reported. Other conformations having the formal properties of minima can be found for the fluorinated compounds, but they are not reported for the sake of simplicity. The distances of the single O-N bond in Å are also in table 1. The SCF minima show a consistent trend towards a moderate increasing of the O-N single bond length with the number of F atoms. However, both DFT and MP2 results predict uncommonly long O-N equilibrium distances. For the F-methyl nitrite conformers, the value got for the O-N bond length is about 1.5 Å at B3LYP and MP2 levels. The O-N bond length values are less similar in the CF2H- and CF3- cases. As discussed above, in the methods section, at this point the authors prefer to rely in the MP2 geometries and energies. As a consequence, the study of the single-electron outer valence ionization energies of two- and three- fluorinated methyl nitrites has been discarded. It can be of some interest to note that, contrarily to what happens with methyl nitrite, in the fluoro-methyl case the anti conformer is found to be more stable than the syn counterpart.
Table 1 Energy (hartree) and O-NO single bond distance for the SCF, MP2 and B3LYP minima (6-311++G(d,p) basis set) of methyl nitrite and fluorinated methyl nitrites.
The IP values according to the Koopmans' theorem and OVGF calculation are reported for anti conformers of methyl and fluoro-methyl nitrite in table 2. The corresponding values for the syn conformers are reported in table 3.
Both tables 2 and 3 include a column with pictorial schemes of the orbitals from which the electron are removed in each one-electron ionization process whose energy is given. These figures can help the reader to figure out the distribution of signs and nodal surfaces around the (essentially planar) C-O-N=O structure. In general, the studied molecular structures have as a whole C1 symmetry, but it can be helpful to distinguish between p-like and s-like MO's according to their behaviour relative to the C-O-N=O plane.
Table 2. Molecular orbitals and vertical ionization energies (eV) for the anti conformers of methyl and fluoro-methyl nitrite.
(§) MO's with significant p-like electron density centered in the F atom.
a MO's denoted according to their s-like or p-like behaviour. Notation for this work. See text for details.
b MO's denoted according to the C1 point group symmetry.
c Koopmans' IP values (6-311++G(d,p) basis set). This work.
d OVGF IP values (6-311++G(d,p) basis set). This work.
Table 3. Molecular orbitals and vertical ionization energies (eV) for the syn conformers of methyl and fluoro-methyl nitrite.
(§) MO's with significant p-like electron density centered in the F atom.
a MO's denoted according to their s-like or p-like behaviour. Notation for the present work. See text for details.
b MO's denoted according to C1 point symmetry group.
c Koopmans' IP values (6-311++G(d,p) basis set). This work.
d OVGF IP values (6-311++G(d,p) basis set). This work.
The HOMO is denoted as sI . The other MO's classified as s are denoted as sII, sIII , and so on, accordingly to their increasing Koopmans' energies. A similar notation is used for p-like MO's. This notation makes easier the task of comparing the results for non-substituted and F-substituted systems, as well as the assignation of the spectra features. The conventional notation based on the C1 (non)symmetry group has been also provided in tables 2 and 3 so that the correspondence of each MO and spectrum peaks with the new notation is simple to set no matter the molecule, the calculation level and the structure under consideration.
Only the occupied MO's that lead to converged poles in the OVGF calculations are reported in tables 2 and 3. All the MO's reported are consecutive in the canonical one-electron energy values (Koopmans). Note, however, that in some cases the order of the ionization energies is changed by the OVGF calculation (see, e.g., the pII and sV MO's in table 2 and the pII and sIII MO's in table 3).
The simulation of the experimental He I -UPS spectrum reported by Wang et al. [11], as it results from the procedure described in the methods section, has been included in figure 1. The same figure shows the calculated simulation of the UPS spectra of non-substituted methyl-nitrite for the syn and anti forms.
The bands of the simulated spectra shown in figure 1 have been labelled A to G. The OVGF assignment of the bands can be obtained from tables 2, 3 and 4 with the help of these labels and the ad hoc notation described above. The assignment on the basis of Koopmans' theorem is not shown for simplicity, but it can be easily established from tables 2 and 3.
The main features of the experimental spectrum [11] can be described as follows (see table 4). 1) The onset of the spectrum is sharp and close to 10.0 eV. 2) The two first bands at 11.03 and 11.83 eV are well resolved. 3) A separated band at 13.50 eV occurs after a gap of ˜1 eV. 4) After the second gap a broad band shows two maxima at 14.75 and 15.44 eV. 5) Two more separated bands of decreasing intensity occur at about 16.8 and 18.5 eV, the last band was not assigned by the authors in reference [11].
All these features are essentially present in the simulation of the experimental spectrum shown in figure 1, even if the last two bands appear as too much intense. All these features are present also in the simulations based in the OVGF results of the syn conformer. They are also present in great part in the OVGF-based simulation for the anti conformer.
The greatest discrepancy between the experimental and the calculated spectra occurs in the intensity of the peak labelled as F. The double intensity of the F peaks in the OVGF spectra is a consequence of the occurrence of two IP values that cannot be resolved under the conditions of the spectra simulation.
Table 4. Descriptive assignment of the main features in the experimental UPS spectrum of methyl nitrite and the calculated UPS spectra. See text for details.
a Spectra features. See figures 1 and 2.
b Assignment and experimental IP values (eV, in parenthesis) as reported by D. Wang et al. in ref [11].
c D and E peaks appear as unresolved for the simulation conditions in the syn case of methyl nitrite.
d A low intensity signal at 18.5 eV appears in the experimental spectrum in ref. [11] that was not assigned by the authors.
Figure 1.Simulated UPS spectra of methyl nitrite according to the procedure described in the text and using data from the experimental spectrum[11] and OVGF calculations (this work)
The predicted spectra for the two conformers of the fluoro-methyl substituted nitrite are shown in figure 2. The simulated spectrum of methyl-nitrite (based on the experimental data) is shown in figure 2 as it was in figure 1, in order to make comparisons easier. The bands in the spectra of the fluorinated systems are labelled A* to G*. In this way, the effects on the spectrum due to fluorination are easily shown and compared to the A to G features in figure 1. These effects are summarized in table 5. The following facts deserve to be pointed out:
1) The outer bands appear displaced towards higher IP's . However, the p-like B* band appears more displaced than the s-like A* band. As a consequence, a deep gap is predicted between the A* and the B* peaks. Note that the B* peak occurs in the region (12.0-13.0 eV) where the first large gap occurred in the spectrum of the non substituted molecule.
2) The bands C* and D* appear closer to each other than the bands C and D in methyl nitrite. The data in table 5 show that this effect is mainly due to the large displacement of the D* band towards smaller IP's in both syn and anti conformers. Note, however, that even for the conformer the gap between C* and D* features is smaller as compared to that between C and D.
3) As a consequence of points 1) and 2), the A* to D* peaks set gathers in the range 10-15 eV, while the A-D peaks of methyl nitrite extends from 10-16 eV
4) Another consequence of the large shift of D* is the prediction of a great gap between the D* and the E* band. Another way of seeing this is to say that, as a consequence of the points above, the gap between the outer valence and the inner valence parts of the spectrum becomes larger. Note also that the E peak appears as unresolved in the syn case in figure 1.
5) The F* and G* features show smaller displacement. These features are predicted too much intense, in particular for the anti conformers where unresolved peaks are obtained.
The errors expected from OVGF calculations should be taken into account in order to discuss the results shown in the section above. For the outermost vertical valence ionization potentials, in the case of molecules having second row atoms (Li-Ne), errors of ±0.2 eV can be expected with the OVGF method [18]. Our basis set does not include f functions, so that we will assume larger errors, say ±0.3 eV [18]. These values are of the same order than the FWHM that we have used for the simulation (0.5 eV).
Figure 2. Simulated UPS spectra of fluoro-methyl nitrite according to the procedure described in the text and using data from the OVGF calculations (this work)
Errors in the inner valence region of the spectra can be significantly larger. In fact, the features concerning the highest IP values do not deserve a detailed discussion because the OVGF predictions, made on the basis of one-electron processes, are much less reliable as one approaches the inner valence region of spectra. Hence, the discussion is focused on the A-D (A*-D*) features of the spectra. All these features, but the B (B*) one (see table 4) can be assigned. Note, however, that the E (E*) feature can be assigned as p-like in the methyl nitrite forms, but as s-like in the fluoro-methyl case.
OVGF and SCF results
It is worth mentioning that a one to one correspondence exists between the MO energies and the OVGF values. The correlation effects decrease the four IP's assigned to A-D (A*-D*) peaks by about 1.4 eV in the methyl-nitrite and about 1.6 eV in the mono substituted forms. Under the conditions of the spectra simulations, this change is about three times the FWHM of the bands. These changes fall in the range from 1.27 to 1.77 eV. Their relevance is not only quantitative because the order of the assignments can change, as it happens for the pII MO of the syn form of methyl-nitrite. It becomes clear that the correlation effects cannot be left out for a realistic simulation of the spectra.
Table 5. Effect of F substitution in the calculated UPS spectra of methyl nitrite as given by the shift in the OVGF ionization potential values (eV).
a See figures 1 and 2.
b mn stands for methyl nitrite
c fmn stands for fluoro-metyl nitrite
d Averaged from -0.44 and -0.96 eV
e Averaged from -0.13 and -0.25 eV
Syn and anti forms
As reported in table 1, the syn conformer appears as the most stable form of methyl-nitrite, while the anti form is found more stable in the fluoro-methyl nitrite.
The differences between the syn and anti simulations show up in figures 1 and 2. In the flourinated molecule, only the A* and the C*-D* peaks are significantly affected by the syn-anti isomerism. Therefore, apart from the shift of the first peak (that implies the shift of the spectrum onset), the only region affected by the conformational changes around the O-N single bond would be that in the range of 13.5 - 15 eV.
The differences between the syn and anti spectra are more relevant for methyl nitrite, in this case, all the peaks are shifted by 0.12-0.35 eV (absolute values). In particular, the C and E features are the only shifted towards smaller IP values, and their shift amount to -0.23 and -0.26 eV respectively.
Note that the first IP, corresponding to the A and A* features in figures 1 and 2, is incremented by ca. 0.2 eV in the syn forms, no matter if the molecule is fluorinated or not. However, the B* peak, assigned to the p-like MO closer to the HOMO, is not affected. This behaviour is predicted by the Koopmans' approach, and confirmed by the correlated OVGF results.
F substitution effects
The changes and general features introduced in the spectrum by the presence of the F atom have been described in detail in the previous section. We will only say here that they are relevant enough to assure that the F-methyl nitrite spectrum can be easily discriminated from that of the non substituted systems. The shift of the B* band by 1.0 eV towards the region of the first deep gap in the methyl nitrite spectrum at 12.5 eV can be a key feature to describe the effect of F substitution.
The OVGF results place properly the onset of the spectrum and its general shape, even if a overall dumping function has been used to simulate the intensity attenuation at large IP values. The changes related to the syn-anti conformerism can be significant, although taking it into account appears to be less relevant in the fluorinated case than in methyl-nitrite one. The changes in the spectrum due to the replacement of an H by a F atom in the methyl nitrite are predicted to be relevant, both in shifts as in the general shape of the spectrum.
The present calculations have been performed with a limited basis set, but the effects related to the F substitution are in most cases larger than the expected errors. However, the effects related to the syn-anti conformerism were found to be smaller than the expected errors. These results could be refined by using larger basis sets that include at least f functions, as the expected errors could, in that case, become smaller that ±0.2.
This research was supported by the Spanish MEC, Spanish GV and European FEDER Funds, (Projects CTQ2004-07768-C02/BQU and GV-INFRA03-047). M.R.E. thanks the spanish GV for a visitor grant (AINV06/069).
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A Special Debut in Dubai
The 458 Speciale, the very latest car in the Ferrari range, today made its official Middle East debut on the opening day of the Dubai International Motor Show.
Unveiling the Maranello sports car in front of the press and public were Giancarlo Fisichella, a Ferrari driver in the FIA World Endurance Championship, Giulio Zauner, General Manager of Ferrari Middle East & Africa and Hossam Hosni, General Manager Luxury Auto of Al Tayer Motors, the exclusive Ferrari importer for the United Arab Emirates.
The new special series car from the Maranello marque, like all Ferraris, features an ensemble of technological innovation which makes this car unique and special, aimed at the most demanding of its sports orientated customers who are looking for maximum excitement at the wheel. Patented by Ferrari and a world first are the innovations regarding the whole of the car, especially the power unit, its aerodynamics and vehicle dynamics, with an even more marked difference to the base model, than on special editions from the past, such as the Challenge Stradale and the 430 Scuderia.
On road and track, the 458 Speciale driver feels part of the vehicle itself, as it delivers instant response to inputs and total control in even the most complex of manoeuvres. All drivers can thus reach a high performance level, living an intense and exciting experience at the wheel of FerrariвАЩs most powerful 8 cylinder engine.
The most powerful aspirated engine (605 cv) and the highest specific power output (135 cv/l) in the history of road-going Ferrari V8 engines, an amazing power to weight ration (2.13 Kg/cv,) aerodynamic efficiency (an E Index of 1.5) and electronic control of the set-up angle (SSC:) these are some, but not all of the characteristics that make this car really Speciale and ensure that it is destined to set the standard for Ferraris of the future.
Alongside the 458 Speciale on the stand are other cars from the Prancing Horse range, such as the FF1, the F12 Berlinetta and the 458 Spider.


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Anosmia, the inability to smell, isn't as well-known as blindness or deafness, but it still affects an estimated two million people in the US. A new breakthrough has cured anosmia in mice... and the human impact could be far greater.
Researchers at the University of Michigan Medical School used a specially modified strain of the common cold virus to cure the condition in mice. The virus was loaded up with the desired DNA sequences, and as the infection ran its course through the mice's body their cells were rewritten. By the time the mice had recovered, they were able to smell again. Senior author Dr. Jeffrey Martens explains:
"Using gene therapy in a mouse model of cilia dysfunction, we were able to rescue and restore olfactory function, or sense of smell. Essentially, we induced the neurons that transmit the sense of smell to regrow the cilia they'd lost. At the molecular level, function that had been absent was restored."
This isn't a minor problem — the mice in the study suffered from birth defects that affected a protein known as IFT88. Problems with thiis protein lead to a lack of cilia, the hair-like structures on the body's cells, which in turn makes the mice more likely to have trouble feeding properly and often leads to early death. A similar birth defect occurs in humans, and it's also usually fatal. What's more, cilia dysfunction is also linked to a whole host of other serious diseases, in particularly polycystic kidney disease.
That's actually where the good news comes in — because the researchers have figured out how to solve this particular cilia-related condition, there's now hope that the same strategy can be used to treat even more serious diseases. Admittedly, there's still a long ways to go before this treatment can be applied to humans, and even then it's likely to be of use primarily for people whose anosmia is genetic rather than a result of sinus, aging, or injury. Still, it's a cool result that might lead to a new kind of non-invasive treatment. Besides, it's high time we start making the common cold work for us rather than against us.
For more, check out the University of Michigan. Image by Dennis Wong on Flickr.


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Posted by Editoress on 01/11/09
Employment Opportunity
Bikefit, one of Canada's leading bicycle retailers is growing again! Located in the heart of Niagara's cycling paradise, we cater to beginners and enthusiasts alike with top brands like Trek and Giant. If you have a passion for cycling and a devotion to first class customer service we want to hear from you.
Tech Centre Manager / Lead Bicycle Mechanic
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Job description:
Reporting directly to the General Manager, the Tech Centre Manager oversees, coordinates, schedules and successfully executes all Tech Centre activities and ensures excellent customer service, quality workmanship and timely delivery.
In addition, the Tech Centre Manager is also responsible for:
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Supervision of all department staff with regards to highly accurate P.O.S. system use and adherence to company policies & procedures
Assisting with hiring, training and motivating Tech Centre staff
Assisting with staff performance evaluations and reports
Inventory management of products and supplies as they relate to the department
Participation in factory training and product knowledge seminars
Involvement in facilitating and organizing seminars and special events for the cycling community
Warranty claims and recovery
Assistance in shipping and receiving as required
Maintaining a clean, organized, safe and hazard free work environment pursuant to the Health and Safety Act
Experience, Knowledge & Qualifications:
Minimum 3 years experience as a professional bicycle mechanic with highly developed skills in wheel building, hydraulic brake and suspension service
Long term employment plans and desire for a better future
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Computer and P.O.S. experience and asset
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Cover letter, resume and salary history to: email@example.com.
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Time to start working on the base again. Haven't had steady workouts since I started tapering for Boston. As a result, mileage has been low and the speed workouts very inconsistant. Great opportunity to change that with nothing but shorter races from meow until the MDI Marathon.
Looking forward to a regular routine again. Today's run was a short, semi-progression on hills. Got it in just before the storm. Second run in the Kinvara 3s and I continue to be very pleased with them.
Ran 5.6 miles @ 7:28/mile pace.
Paved and dirt roads.
Very hilly.
Around 60 degrees, overcast humid.
Saucony Kinvara 3, shorts, short sleeved shirt.


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Back when we changed the format for submitting questions, I strongly encouraged people who were currently experiencing a crisis to call a hotline or helpline and talk to a friendly person rather than wait for me to sort through the bulging email box and get to their question. The questioners who wanted help composing their suicide notes, the questioners who had possibly just been sexually assaulted and wanted me to tell them if they really had been, the questioners who were literally holding ice packs to their faces in the aftermath of partner violence were definitely 100% Above My Pay Grade. It was unhelpful and dangerous for them to wait; it was overwhelming for me to try to run a crisis hotline out of my email.
The excellent PFC Marie pointed out that the prospect of calling a hotline was daunting and wouldn't have necessarily occurred to her when she was in crisis mode, and suggested that we find someone who had worked on one to demystify the process. Thankfully, one of our community members stepped forward. Their experience is obviously not universal to every kind of hotline/helpline, but hopefully it will help people feel less nervous about picking up the phone. Hopefully other volunteers will weigh in and give a diversity of experiences and what to expect. The poster has asked to remain anonymous for this post, which is kind of the point of hotlines when you think about it.


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Profiles in Profiteroles: Champions, to your corners
Jordan Lynch, pinballer of the year. (AP)
Our weekly highlight show of lesser FBS luminaries. Non-AQs and independents, be welcome. WE HAVE MUCH TO DISCUSS.
• On teams about to move themselves outside our purview. Like we said this morning, we had no sooner finished updating our magnificent work of college football realignment art than word came down we might need to add Middle Tennessee State to it. And right as we were wrapping up this here column, Florida Atlantic joins the fray, chasing FIU to Conference USA. Consider this another plea for a dead period in conference realignment, for the sake of everyone's collective multitasking abilities, at least until the bowls are over. What on earth else are we going to talk about in February if we get all this conference-hopping sorted out before Christmas?
And what to do with some of these teams going forward? We have a while to figure it out, obviously, but how to cover this ballooning middle class created by the sinking of the Big East? Will the Blue Raiders graduate from Profiterole-dom as Temple did last year? We'll probably dedicate way more thought to this than we should; but, again, best to save that for the offseason when we have nothing better to do.
• Conference races drawing to a close. Where we're at heading into that weird hybrid weekend of regular and postseason games: Kent State and Northern Illinois meet Friday night in Detroit for the MAC title game. Tulsa hosts Central Florida this Saturday for the C-USA championship. The Mountain West remains deadlocked in that wacky three-way tie between San Diego State, Fresno State and Boise State, with only the Broncos' Saturday date with Nevada standing any chance of breaking it. The top two teams in the Sun Belt, Arkansas State and Middle Tennessee, play a final regular-season game Saturday that may as well be the conference title game. Utah State has clinched the WAC title outright with last week's victory over Idaho. And Army and Navy will meet a week from Saturday for the right to hoist the Commander-in-Chief's Trophy, with Air Force out of the race entirely for the first time since 2005.
• Bowltyme! Stewart Mandel's latest postseason projections can be found here, along with a freshly-updated chart listing every accepted bowl invitation. Profiteroles playing this holiday season include Nevada in the New Mexico Bowl, Utah State in the Potato, San Diego State and BYU in the Poinsettia, Louisiana in the New Orleans, SMU in the Hawaii, Air Force in the Armed Forces and Navy in the Fight Hunger.
Profiles in ownage
• Colby Cameron, QB, Louisiana Tech. Freshly minted newest honoree of the Touchdown Club of Columbus, which just announced Cameron will be presented with the Sammy Baugh Award in February. (Last year's winner: Profiteroles favorite Case Keenum.) The timing of the announcement is somewhat awkward, as Cameron was intercepted three times in his last game by San Jose State DB Bené Benwikere, the reigning Walter Camp Defensive Player of the Week.
• Derek Carr, QB, Fresno State. Helped the Bulldogs hang onto their Mountain West championship tie with a 452-yard, four-touchdown performance against Air Force.
• Shane Carden, QB, East Carolina. 439 yards and six touchdowns in the highest-scoring game in Conference USA history, ECU's 65-59 double-overtime defeat of Marshall.
• Cody Hoffman, WR, BYU. Caught five touchdown passes against New Mexico State, just the second time this season an FBS player has hit that mark.
• Antonio Andrews, RB, Western Kentucky. Third consecutive game with 300+ all-purpose yards, including 230 rushing yards on 25 carries against North Texas. Third on the NCAA's all-time single-season yardage list, trailing some guy named "Barry Sanders" by 274.
• Adam Muema, RB, San Diego State. 255 rushing yards and four touchdowns versus Wyoming.
• Kevin Byard, DB, Middle Tennessee. 77-yard pick-six, a forced fumble, a pass breakup and a second interception against Troy.
• Trent Voss, LB, Toledo. 12 tackles, 1.5 sacks, 2.5 TFL, one interception and two pass breakups against Akron. And he's a freshman. Sorry, MAC West.
• Ja'Gared Davis, LB, SMU. Accounted for an interception, a blocked punt and a fumble recovery in the Mustangs' upset of Tulsa.
• Jeremy Eddington, KR, Rice. 210 yards on four returns against UTEP, including a 97-yard return for a score. Before this week, Rice had not seen a kickoff returned for a touchdown since 1984.
Not sure if serious
• Kolton Browning's victory formation fumble. "The contest started rather inauspiciously," reads Louisiana-Monroe's official game recap, but not nearly as inauspiciously as it ended: "On third and 13, with FIU out of timeouts and 28 seconds on the clock, Browning was hit while in victory formation and the ensuing fumble was recovered by FIU's Josh Forney. After an incomplete pass, Hilliard found receiver Willis Wright for a 56-yard touchdown pass down the visitors sideline. Griffin's point after tied the game at 17, and forced overtime." Todd Berry had, by this point, already received the victory Gatorade shower, but at least he didn't have to watch Mario Cristobal get a second one.
• Ross Parmley's suspension. Here's a bunch of words you don't ever want to appear in the same sentence as your name if you're an athletic department official: "Ten months after becoming the University of Tulsa's athletic director, Ross Parmley was placed on paid administrative leave Tuesday after having been described by the FBI as an 'admitted gambler.'"
Walking Dead Watch
Southern Miss suffers one of the cruelest indignities in college football, at the tail end of a season full of them: A double-digit loss to Memphis. 0-12 is in the books, and Ellis Johnson is hitting the bricks.
Case Keenum Memorial Pinballin' Hi-Score
After this year, we might have to rename it after Jordan Lynch. After Friday's 49-7 obliteration of Eastern Michigan, Northern Illinois' Chandler Harnish replacement part has put together a first starting season to be goggled at: 1,611 yards rushing. 16 rushing touchdowns. 2,750 yards passing. 23 passing touchdowns. Four interceptions. 4,362 yards of total offense. And a punt, just for funsies.
Thing UTEP did this week
Sent off their retiring coach with a "Mike Price Appreciation Day" in the Sun Bowl ... that culminated in a loss to Rice. Never change, UTEP.
With no more schedule AQ-on-non-AQ games before bowl season, we retire the 2012 scoreboard for the regular season at 22-86. Well done, lads.


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First-Year Life
What's First-Year Life Like at AU?
The first year of college is one of excitement, decision-making and fun. It is very common for you to be uncertain about what to expect during your first year at AU. Below are answers to common questions students have on starting college:
What classes are offered each semester?
The Undergraduate Course Catalog provides you with information about the requirements of all majors and minors, as well as general education requirements. Students can also find detailed information about dropping and adding courses, tuition charges, billing dates and registration policies in the catalog. You can also reference the brochure for policies that will govern your academic program while you pursue your degree at AU.
When will I get my class schedule?
All new students will receive a copy of their schedule when registering for classes with their academic advisor at AU4U summer orientation and registration. For an additional copy, class schedules can be found online through WebAdvisor.
What are general education classes?
General education classes are required for all undergraduate students to take in order to have a well-rounded education at AU. These classes teach you skills like writing, critical thinking and communicating your ideas more effectively. General education classes supplement your major class requirements.
In the undergraduate course catalog, what does IDS stand for?
IDS stands for "Interdisciplinary Studies." These classes focus on wellness, diversity and career development. First-year students will learn valuable skills to help them succeed in college and their future careers. The courses are taught in small groups by teams of faculty, professional staff and peer advisors.
How do I get my student ID Card? What do I do if I lost it?
All Aurora University students are required to have an ID card. Resident students will be provided with their ID cards when they check into the residence halls at the start of the semester. Commuter students can obtain their card from the Office of Campus Public Safety. The ID card serves the following purposes:
- Identification as a member of the Aurora University community.
- Dining card for meals at the AU dining locations.
- Admittance into the main entrance of your residence hall.
- Privilege of checking out books from the Charles B. Phillips Library.
During the school year, replacement student IDs can be made at Office of Campus Public Safety, 1501 Southlawn. You will need a driver's license or another photo ID as proof of identification and proof of your student ID number. Please note that a replacement fee is charged to those students who lose or damage their cards.
What kind of computer should I get?
Having a computer is not mandatory. Many students take advantage of the computer labs available on campus and in the library. It costs nothing to use a computer or printers located in the labs.
If you can afford to purchase a computer, many students find laptops to be the most convenient to use. Laptops give you the freedom to use your computer anywhere on campus, whether that is in your dorm room or at The Spartan Spot with a study group. WiFi connections are available across campus.
I'm struggling in a class. What can I do?
If you are struggling in any class, the first thing you should do is talk to your professor after class or schedule an appointment with them outside of class. Faculty may be able to offer guidance or recommend you to make a tutoring appointment in the Academic Support Center.
I'm not a good test-taker. What should I do?
Set up tutoring sessions in the Academic Support Center, or study with a group of classmates. You should also talk to your professors and ask them how you can better prepare for their tests.
Where do I get my books for class?
The Campus Bookstore sells course materials, school supplies and reference books. You may visit the Bookstore's website purchase books. If preferred, you may rent textbooks online by choosing the ― "Textbooks Rental" tab on the bookstore's site.
Your Questions are Answered
There are so many questions about the first year of college. This Web site gives you information about many aspects of your life as a first-year student, from class selection to living on campus. Surf these pages and hopefully you'll get a feel for what life is like at AU as well as get the answers you need.
We have a person who is dedicated to first-year students. Brynn Landwehr's job is to answer your questions. Her door (310 Eckhart Hall) is always open. Her phone (630-844-7861) is always available, and she's always logged on (email@example.com). Contact her directly and she will answer your question or find out for you.
To have more of your questions answered, read the First-Year F.A.Q.
Academic Advising is Key
The foundation of the first-year program is academic advising. Your advisor will be your academic mentor through your first-year of college and have a keen understanding of what makes a successful college student. Through your relationship with your academic advisor, you will be able to explore career options for your future and help you find where your path in life.
Peer Advisors Link You to Campus
Another mentor to help you along your way will be your peer advisor. Peer advisors are upper-class students who lead AU4U in the summer and help you as a new student once you arrive on campus. Peer advisors consider themselves "instant friends" who can show you what life is like as a first-year student.
Contact Us
Brynn Landwehr
First Year Academic Advisor
Visit: 310 Eckhart Hall
Call: 630-844-7861
E-mail: email@example.com


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I asked him if he had seen the sun lately.
He looked at me quizzically as he handed back my cash. His teenaged face said it all – this lady's a wacko for sure.
"Well, yeah," he said. "I've been in and out all day."
"So you've seen it, then?"
"The sun?" he asked, forehead wrinkling in puzzlement.
At this point, I'm pretty sure he wanted me to go away. Sooner rather than later.
I whipped out my phone and pointed at the screen.
"Yes, the sun!" I showed him the images I had captured. "Isn't it amazing??"
By now, I was holding up the line. And, the cashier didn't mind. Neither did the people behind me who hadn't seen it either.
A gorgeous circular band encompassing the sun. A golden ring of light. A halo.
Brilliant. Miraculous. Captivating.
Hanging in the sky for all to see. Within plain sight.
Yet, almost no one saw – including me.
If my mother hadn't called and asked me to look up, I would have missed the glowing band altogether. I was so focused on what was in front of my nose. My tasks, my chores, my appointments. The traffic, my child's endless requests, what to have for dinner (as usual).
I didn't see anything.
Which begs the question … what other things might we all be missing?
When we fail to look up. Down. Around. Inside.
When we fail to take a moment to sit with what is.
When we fail to notice.
What might be seen if we looked, took a moment, noticed?
The brilliant possibilities.
The miraculous chances.
The captivating opportunities.
Look around you. Are there things hanging in plain sight waiting for you to see them?
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This treatment is based on one by Prof. Ernie Davis.
Tannenbaum suggests that the WSClock Page Replacement Algorithm is a natural outgrowth of the idea of a working set. However, reality is less clear cut. WSClock is actually embodies several ideas, one of which is connected to the idea of a working set. As the name suggests another of the ideas is the clock implementation of 2nd chance.
The actual implemented algorithm is somewhat complicated and not a clean elegant concept. It is important because
Since the algorithm is complicated we present it in stages. As stated above this is an important algorithm since it works well and is used in practice. However, I certainly do not assume you remember all the details.
We start by associating a node with every page loaded in memory (i.e., with every frame given to this process). In the node are stored R and M bits that we assume are set by the hardware. (Of course we don't design the hardware so really the R and M bits are set in a hardware defined table and the nodes reference the entries in that table.) Every k clock ticks the R bit is reset. So far this looks like NRU.
To ease the explanation we will assume k=1, i.e., actions are done each clock tick.
We now introduce an LRU aspect (with the virtual time approximation described above for working set): At each clock tick we examine all the nodes for the running process and store the current virtual time in all nodes for which R is 1.
Thus, the time field is an approximation to the time of the most recent reference, accurate to the clock period. Note that this is done every clock tick (really every k ticks) and not every memory reference. That is why it is feasible.
If we chose as victim the page with the smallest time field, we would be implementing a virtual time approximation to LRU. But in fact we do more.
We now introduce some working set aspects into the algorithm by first defining a time constant τ (analogous to ω in the working set algorithm) and consider all pages older than τ (i.e., their stored time is earlier than the current time minus τ) as candidate victims. The idea is that these pages are not in the working set.
The OS designer needs to tune τ just as one would need to tune ω and, like ω, τ is quite robust (the same value works well for a variety of job mixes).
The advantage of introducing τ is that a victim search can stop (and the I/O begin) as soon as a page older than τ is found.
If no pages have a reference time older than Tau, then the page with the earliest time is the victim.
Next we introduce the other aspect of NRU, preferring clean to dirty victims. We search until we find a clean page older than τ, if there is one; if not, we use a dirty page older than τ. As before, if there are no clean pages older than τ, we evict the oldest page
Now we introduce an optimization similar to prefetching (i.e., speculatively fetching some data before it is known to be needed). Specifically, when we encounter a dirty page older than τ (while looking for a clean old page), we write the dirty page back to disk (and clear the M bit, which Tanenbaum forgot to mention) without evicting the page, on the presumption that, since the page is not in (our approximation to) the working set, this I/O will be needed eventually. The down side is that the page could become dirty again, rendering our speculative I/O redundant.
Suppose we've decided to write out old dirty pages D1 through Dd and to replace old clean page C with new page N.
We must block the current process P until N is completely read in, but P can run while D1 through Dd are being written. Hence we would desire the I/O read to be done before the writes, but we shall see later, when we study I/O, that there are other considerations for choosing the order to perform I/O operations.
Similarly, suppose we can not find an old clean page and have decided to replace old dirty page D0 with new page N, and have detected additional old dirty pages D1 through Dd (recall that we were searching for an old clean page). Then P must block until D0 has been written and N has been read, but can run while D1 through Dd are being written.
We throttle the previous optimization to prevent overloading the I/O subsystem. Specifically we set a limit on the number of dirty pages the previous optimization can request be written.
Finally, as in the clock algorithm, we keep the data structure (nodes associated with pages) organized as a circular list with a single pointer (the hand of the clock). Hence we start each victim search where the previous one left off.


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admin, January 18th , 2020.
Tray ceilings are a contemporary architectural feature that have ended up in way too many traditional style homes. They try to fill our need for unique detail in our otherwise generic interiors. A tray ceiling, which is an inverted or recessed ceiling, creates the illusion of height. Depending on the type of wood and colors you choose, you can make the room look traditional, contemporary or even rustic. Wooden planks or reclaimed wood are great options for that rustic effect.
The dining room seems to be where all the entertaining happens. Whether it is for the immediate family, holiday dinners or intimate romantic dinners, the dining room is a special room. When decorating your dining room, we often forget about the flooring and the area rug that goes under the table. Believe it or not, the perfect area rug can make your room feel casual or formal, just by changing the rug. Here are tips for choosing the right one for your home.
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text: Following an incredibly bourgeois (and yes, Cathy Horyn, stunningly beautiful) Downton Abbey-esque showing for Louis Vuitton at Paris Fashion Week complete with a fully functioning locomotive, women in oversized hats, and the Marie Antoinette-worthy assertion that "No girl will carry a bag this season, it will be carried for her," legendary designer Marc Jacobs showed up at the opening of his own exhibit at the Musée des Arts Décoratifs wearing, by all accounts, a fairly casual (but bright!) pink polo dress. Jacobs' nontraditional look inspired at least one fashion writer in the tri-state area to wonder: who else in fashion has crossed gender lines in the name of haute couture?