# 1 Low-energy part of the eigenvalue spectrum of the PHM [periodic boundary conditions, SMA]. Eigenvalues in (c) and (d) are two-fold degenerate.

Local mode behaviour in quasi-1D CDW systems   
H. Fehske<sup>a</sup>, G. Wellein<sup>b</sup>, H. Büttner<sup>a</sup>, A. R. Bishop<sup>c</sup>, and M. I. Salkola<sup>d</sup> <sup>a</sup>Physikalisches Institut, Universität Bayreuth, D-95440 Bayreuth, Germany <sup>b</sup>Regionales Rechenzentrum Erlangen, Universität Erlangen, 91058 Erlangen, Germany <sup>c</sup>MSB262, Los Alamos National Laboratory, Los Alamos, NM 87545, USA <sup>d</sup>Superconductor Technologies Inc., Santa Barbara, CA 93111, USA Abstract   
We analyze numerically the ground-state and spectral properties of the three-quarter filled Peierls-Hubbard Hamiltonian. Various charge- and spin-ordered states are identified. In the strong-coupling regime, we find clear signatures of local lattice distortions accompanied by intrinsic multi-phonon localization. The results are discussed in relation to recent experiments on MX chain \[-PtCl-\] complexes. In particular we are able to reproduce the observed red shift of the overtone resonance Raman spectrum. Keywords: charge density wave, localized lattice distortions, polarons, MX-chain compounds    
Inspired by the recent observation of intrinsically localized vibrational modes in halide-bridged transition metal \[-PtCl-\] complexes , we study strong coupling effects between electronic and lattice degrees of freedom on the basis of a two-band, 3/4-filled Peierls-Hubbard model (PHM)

$``$ $`=`$ $`t{\displaystyle \underset{i,j\sigma }{}}c_{i\sigma }^{}c_{j\sigma }+{\displaystyle \underset{i\sigma }{}}\epsilon _in_{i\sigma }+{\displaystyle \underset{i}{}}U_in_in_i`$ (1)   
$`+\lambda _I(b_I+b_I^{})(n_1+n_3n_2n_4)+\mathrm{}\omega _Ib_I^{}b_I`$   
$`+\lambda _R(b_R+b_R^{})(n_2n_4)+\mathrm{}\omega _Rb_R^{}b_R.`$   
In (1), the $`c_{i\sigma }^{[]}`$ are fermion operators, $`n_{i\sigma }=c_{i\sigma }^{}c_{i\sigma }`$, and $`b_R^{[]}`$ and $`b_I^{[]}`$ are the boson operators for the Raman active (R) and infrared (I) optical phonon modes with bare phonon frequencies $`\omega _R`$ and $`\omega _I`$. With regard to the quasi-1D charge density wave (CDW) system $`\{[\mathrm{Pt}(\mathrm{en})_2][\mathrm{Pt}(\mathrm{en})_2\mathrm{Cl}_2](\mathrm{ClO}_4)_4\}`$ (en= ethylenediamine), subsequently abbreviated as PtCl, the Pt (Cl) atoms are denoted by the site index $`i=2,\mathrm{\hspace{0.17em}4}`$ ($`i=1,\mathrm{\hspace{0.17em}3}`$). The CDW state is built up by alternating nominal $`\mathrm{Pt}^{+4}`$ and $`\mathrm{Pt}^{+2}`$ sites with a corresponding distortion of Cl<sup>-</sup>-ions towards $`\mathrm{Pt}^{+4}`$. To model the situation of a 3/4-filled charge transfer insulator within a single-mode approach (SMA), we only include the R-($`\nu _1`$)-mode with $`\mathrm{}\omega _R=0.05`$ , and parametrize the site energies by $`\mathrm{\Delta }=(\epsilon _{\mathrm{Pt}}\epsilon _{\mathrm{Cl}})/t=1.2`$ and the Hubbard repulsions by $`U_{\mathrm{Pt}}=0.8`$ and $`U_{\mathrm{Cl}}=0`$ (all energies are measured in units of $`t`$). Alternatively, we employ a more realistic double-mode approach (DMA), using $`\mathrm{}\omega _I=0.06`$ for the I-($`\nu _2`$)-mode .

The ground-state and spectral properties of the four-site PHM are determined by finite-lattice Lanczos diagonalization that preserves the full dynamics of the phonons .

Figure 1 shows the variation of the lowest energy states as a function of the electron-phonon coupling. In the weak-coupling region, the ground-state is basically a zero-phonon state (cf.

Fig. 2 a) and the peaks in Fig. 1 (a) correspond to multiples of the fundamental phonon frequency $`\omega _R^{(1)}`$. As $`\lambda _R`$ increases a strong mixing of electron and phonon degrees of freedom takes place, and finally the lowest states with total momentum $`K=0`$ and $`K=\pi `$ become nearly degenerate. In this limit a non-linear lattice potential stabilizing so-called intrinsically localized vibrational modes (ILMs) is self-consistently generated .

A prominent feature of these bound states is their strong anharmonic redshift, resulting from the attractive interaction of Raman phonon quanta located at the same PtCl<sub>2</sub> unit. The calculated red shift, $`r_n=[n\omega _R^{(1)}\omega _R^{(n)}]/\omega _R^{(1)}`$ with $`\omega _R^{(n)}=(E_nE_0)`$, of the (doublet) overtones shown in Fig. 1 (c) is successfully compared to experimental data probed by resonance Raman scattering (see Tab. 1). To elucidate the different nature of the ground state in the weak- and strong-coupling regimes, several characteristic quantities listed in Tab. 2. Obviously the self-localization transition is accompanied by significant changes in the spin- and charge correlations. As can be seen from the weight of the $`m`$-phonon state in the ground state, $`|c_0^m|^2`$ , depicted in Fig. 2, the appearance of the $``$-$``$-$``$-$``$ configuration is related to large occupation numbers of the localized vibrational (R) mode.

To summarize, the numerical results obtained for the PHM provide strong evidence for the existence of a dynamical spatial localization of vibrational energy (ILM) in MX solids, due to high intrinsic nonlinearity from strong electron lattice coupling.

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2. S. P. Love et al., Phys. Rev. B 47 (1993) 11107.
3. B. Bäuml et al., Phys. Rev. B 98 (1998) 3663.