Ab initio electron propagators in molecules with strong electron-phonon interaction. I. Phonon averages

Ab initio electron propagators in molecular systems with strong electron-electron and electron-phonon interactions are considered to study molecular electronic properties. This research is important in electron transfer reactions where the electron transition is not considered any longer as a single electron transfer process or in temperature dependences of current-voltage characteristics in molecular wires or aggregates. To calculate electron Green's functions, the authors apply a small polaron canonical transformation that intrinsically contains strong electron-phonon effects. According to this transformation, the excitation energies of the noninteracting Hamiltonian are shifted down by the relaxation (solvation) energy for each state. The electron-electron interaction is also renormalized by the electron-phonon coupling. For some values of the electron-phonon coupling constants, the renormalized Coulomb integrals can be negative resulting in the attraction between two electrons. Within this transformation, they develop a diagrammatic expansion for electron Green's function in which the electron-phonon interaction is included into the multiple phonon correlation functions. The multiple phonon correlation functions are exactly found. It is pointed out that Wick's theorem for such correlation functions is invalid. Consequently, there is no Dyson equation for electron Green's functions. The proposed approach can be considered for future method developments for quantum chemical calculations that include strong nonadiabatic (non-Born-Oppenheimer) effects.     

Roles of inter- and intramolecular vibrations and band-hopping crossover in the charge transport in naphthalene crystal

We calculate the hole and electron mobilities in naphthalene crystal from 10 to 300 K within the framework of the Holstein-Peierls model coupled with first-principles density-functional-theory-projected tight-binding band structures. All the electron-phonon coupling constants, including both local and nonlocal parts for inter- and intramolecular vibrations, have been taken into considerations through density functional theory. The band-hopping crossover transition temperature for the electron transport in the c' axis is calculated to be around 23 K. We have identified a few high frequency intramolecular vibrations which are very important to the charge transport in naphthalene crystal due to their comparatively large electron-phonon coupling constants. However, their contributions to the temperature dependence of mobility are minor because of the small phonon occupations and small nonlocal coupling strengths. The low frequency intermolecular modes (longitudinal optical modes) are found to be the major contributions to the temperature dependent charge transfer properties in naphthalene crystal. Even though the calculated qualitative temperature dependence is in agreement with experiment, the predicted absolute mobility is about one to two orders of magnitude larger.     

Geometry, phase stability, and electronic properties of isolated selenium chains incorporated in a nanoporous matrix

We report the fabrication process of isolated one-dimensional Se chains incorporated in the matrix of AlPO4-5 single crystals and the experimental investigation of the geometry, phase stability, electronic properties, and electron-phonon coupling effect of these Se chains. The structure of the helical Se chains inside the channels is discussed on the basis of X-ray scattering measurements. Thermal analysis and temperature-dependent micro-Raman measurements show that Se single chains are flexible and can convert from a weak distorted phase into another phase with strongly disordered structure ("melting" state) around 340 K. Since the electrons are confined in the one-dimensional channels, the absorption band of the Se chain is obviously blue shifted compared with that of trigonal Se. With increasing temperature, this band shifts linearly to the lower energy side, in sharp contrast to the nonlinear temperature coefficient of trigonal Se, which is attributed to the greatly diminished interchain interaction and the weakening of the electron-optical phonon coupling in a low-dimensional system. In the vicinity of the absorption band, both first-order and second-order Raman signals for the Se chain are enhanced, due to the strong electron-phonon coupling when the excitation laser energy matches the electronic transition in isolated Se chains.     

Differing applications of Raman scattering to liquid crystals

An overview of the differing possibilities offered by Raman scattering in the study of liquid crystals is given, together with a few experimental examples of the least studied phenomena. Among them, changes in the intrinsic Raman polarizabilities and phonon self-energies as a function of temperature which provide, in principle, an experimental method for the study of coexisting and/or inhomogeneous phases through Raman imaging. We show that the C-H in-plane deformation mode of the phenyl rings is particularly suited to monitor both intrinsic scattering efficiencies and frequency changes. This mode is present in a large family of liquid crystal compounds and we present evidence indicating that the origin of these changes is its electron-phonon coupling to the lowest allowed electronic transition in the ultraviolet.     

Differing applications of Raman scattering to liquid crystals

An overview of the differing possibilities offered by Raman scattering in the study of liquid crystals is given, together with a few experimental examples of the least studied phenomena. Among them, changes in the intrinsic Raman polarizabilities and phonon self-energies as a function of temperature which provide, in principle, an experimental method for the study of coexisting and/or inhomogeneous phases through Raman imaging. We show that the C-H in-plane deformation mode of the phenyl rings is particularly suited to monitor both intrinsic scattering efficiencies and frequency changes. This mode is present in a large family of liquid crystal compounds and we present evidence indicating that the origin of these changes is its electron-phonon coupling to the lowest allowed electronic transition in the ultraviolet.     

The effect of spin-orbit coupling on the surface dynamical properties and electron-phonon interaction of Tl(0001)

We present an ab initio study of the effect of spin-orbit coupling on the dynamical properties of the Tl(0001) surface as well as on the electron-phonon interaction at the surface. The calculations based on density-functional theory were carried out using a linear response approach and a mixed-basis pseudopotential method. It is shown that the spin-orbit effects on the phonon spectrum and the electron-phonon interaction at the Fermi level of the surface are weak but conspire to a reduction in the electron-phonon coupling strength by 16%.     

Ba1－xSrxTiO3的Sol-gel法制备与结构相变研究

采用sol-gel法制备了钛酸锶钡(Ba1－xSrxTiO3)．用XRD、DSC、Raman等表征技术研究了Ba1－xSrxTiO3的晶体结构和相变行为.结果表明,随着锶含量的增加,晶胞体积逐渐减小,c/a趋近于1,相变温度降低,相变热减少,相变弥散性增强,且存在热滞现象.Raman光谱发生有趣变化,当x=0.30时,室温下发生结构相变, Ba1－xSrxTiO3以立方相为主要存在相,相变具有有序-无序特征.     

Optical absorption of semiconducting and metallic nanospheres with the confined electron-phonon coupling

We study the optical absorption, especially the (far-) infrared absorption by phonons, of semiconducting and metallic nanospheres. In the nanoscopic sphere, phonons as well as states of electronic excitations are quantized by confinement. It is also known that in the nanoscopic geometry, the confined electron-phonon interaction has a different form from the usual one in the bulk. First, we analyze the phonon and electron contributions to the dielectric response of nanospheres like epsilon(q,omega)=epsilon(ph)(q,omega)+epsilon(el)(q,omega) or 1epsilon(q,omega)=1epsilon(sc-ph)(q,omega)+1epsilon(el)(q,omega) from the confined electron-phonon interaction for three cases: the intrinsic semiconductor, the doped semiconductor, and the metal. From the dielectric response, the optical absorption spectra are calculated within the semiclassical framework concentrating on the (far-) infrared region and compared to the spectra without imposing confinement. Nontrivial differences of the spectra with confined phonons stem from two features: the electron-phonon coupling matrix has a different form and the phase space q of the confined phonon is reduced because of its quantization to q(n). Finally, size distribution effects in an ensemble of isolated nanospheres are briefly discussed. Those effects are found to be important in metallic spheres with rapid sweepings of resonances by a small change of the sphere size.     

Enhanced resonant raman scattering and electron-phonon coupling from self-assembled secondary ZnO nanoparticles

Self-assembled secondary ZnO nanoparticles, recognized with the agglomeration of crystalline subcrystals, are successfully synthesized by a simple sol-gel method. TEM images display that one artificial cluster behaves in a single-crystal-like wurtzite structure because subcrystals coagulate as the same crystal orientation. Moreover, from the resonant Raman scattering, the as-grown sample exhibits phonon red shift; meanwhile, the coupling strength between electron and longitudinal optical phonon, determined by the ratio of second- to first-order Raman scattering cross sections, diminishes compared with the samples after postannealing at 350 and 500 degrees C. The size dependence of electron-phonon coupling is principally as a result of the Fr?hlich interaction.     

Spectral characteristics of zero-phonon transitions in crystal impurities: A diagrammatic approach

The zero-phonon line shape of a localized transition in a crystal is treated by use of a general interaction between the local transition and the lattice phonons with the harmonic approximation. The theory is carried out to infinite order perturbation by diagrammatic techniques and is thus valid for arbitrarily large phonon coupling. Within our model it is found that the spectral characteristics of the zero phonon line and their temperature dependence are due to resonant Raman-ike phonon scattering processes which cause a decay of the phase coherence of the excitation. The line shape due to this mechanism is found to be lorentzian, and its width increases with temperature, but is zero at 0 K. The line position is also a function of temperature.     

A theoretical study on the temperature dependence of zero-field splitting for the tetragonal Cr3+ center in MgO crystal

This paper reports a detailed theoretical calculation of the temperature dependence of zero-field splitting D (characterized by ΔD(T)=D(T)-D(0)) for the tetragonal Cr3+ center in MgO crystal by considering both the static contribution due to the thermal expansion of Cr3+ center and the vibrational contribution caused by electron-phonon (including the acoustic and optical phonons) interaction. The vibrational contribution due to the acoustic phonon is calculated using the long-wave approximation similar to the study on the specific heat of crystals and that due to optical phonon is estimated using the single-phonon model. The calculated results are in reasonable agreement with the experimental values. From the calculation, it is found that the static contribution ΔDstat(T) (which is often regarded as very small and is neglected in the previous papers) is larger than the vibrational contribution ΔDvib(T) and so the reasonable studies of temperature dependence of zero-field splitting should take both the static and the vibrational contributions into account.     

Spin-dependent electron-phonon interaction in SmFeAsO by low-temperature Raman spectroscopy

The interplay between spin dynamics and lattice vibration has been suggested as an important part of the puzzle of high-temperature superconductivity. Here, we report the strong interaction between spin fluctuation and phonon in SmFeAsO, a parent compound of the iron arsenide family of superconductors, revealed by low-temperature Raman spectroscopy. Anomalous zone-boundary-phonon Raman scattering from spin superstructure was observed at temperatures below the antiferromagnetic ordering point, which offers compelling evidence on spin-dependent electron-phonon coupling in pnictides.     

Phonon-induced surface charge density oscillations in quantum wells: a first-principles study of the (2 × 2)-K overlayer on Be(0001)

Density functional perturbation theory has been applied to study the surface vibrations of (2 × 2)-K monolayer on the Be(0001) surface. We present the full phonon dispersion curves along the high symmetry directions of the surface Brillouin zone (SBZ) together with the layer-projected phonon density of states and the phonon-induced surface charge density oscillations at Γ and M for the alkali SV and L modes. Surprisingly, at the M point, the L-phonon displacements produce a more pronounced perturbation on the surface charge density than the SV-phonon displacements. These results apparently solve the long-standing question regarding helium atom scattering (HAS) experiments performed on the similar system (2 × 2)-K on graphite, where the alkali SV phonon mode is not observed. Moreover, this result confirms the previous finding that HAS from free-electron metal surfaces probes directly the phonon-induced charge density oscillations and the related electron-phonon interaction.     

Electron-phonon interaction for semiconductors with narrow conductivity zones

The role of various types of electron-phonon interaction in processes of electron transfer in organic semiconductors is examined and estimated. Allowance has been made for inelastic electron scattering, which is extremely significant for systems with narrow zones. The way in which inelastic scattering and changeover processes influence the establishment of the relaxation mechanism has been examined. The influence of the nonequilibrium nature of the phonon distribution function on the phenomena of transfer has been studied.     

Ultrafast electron relaxation dynamics in coupled metal nanoparticles in aggregates

We report the effect of aggregation in gold nanoparticles on their ultrafast electron-phonon relaxation dynamics measured by femtosecond transient absorption pump-probe spectroscopy. UV-visible extinction and transient absorption of the solution-stable aggregates of gold nanoparticles show a broad absorption in the 550-700-nm region in addition to the isolated gold nanoparticle plasmon resonance. This broad red-shifted absorption can be attributed to contributions from gold nanoparticle aggregates with different sizes and/or different fractal structures. The electron-phonon relaxation, reflected as a fast decay component of the transient bleach, is found to depend on the probe wavelength, suggesting that each wavelength interrogates one particular subset of the aggregates. As the probe wavelength is changed from 520 to 635 nm across the broad aggregate absorption, the rate of electron-phonon relaxation increases. The observed trend in the hot electron lifetimes can be explained on the basis of an increased overlap of the electron oscillation frequency with the phonon spectrum and enhanced interfacial electron scattering, with increasing extent of aggregation. The experimental results strongly suggest the presence of intercolloid electronic coupling within the nanoparticle aggregates, besides the well-known dipolar plasmon coupling.     

The exciton—phonon interaction for triplet exciton bands of organic solids: An experimental and theoretical study

Very high resolution optical data on the temperature dependences of the Davydov component absorption profiles and polarization dependent one-phonon structures associated with the lowest triplet exciton band of anthracene are presented along with a theoretical framework for their interpretation. The interpretation of the one-particle exciton—phonon transitions involving both one-phonon creation and annihilation (cold and hot phonon transitions) is entirely consistent with the analysis of the T-dependent dephasing of the lowest zero-phonon Davydov transition in terms of two mechanisms: delocalized exciton—delocalized phonon scattering operative for the low frequency (< 30 cm^?) phonons which undergo no lattice distortion and: Raman like phonon scattering operative for the higher frequency phonons which do. It is the latter which leads to the identical T² linewidth dependences of the two Davydov components in the high T limit. The former scattering is dominant at the lowest temperatures. In addition, the, marked and polarization dependent mirror symmetry breakdown between the hot and cold one-particle transitions can be nicely understood in terms of interferences occurring between the Condon and phononic (from the dependence of the pure exciton transition dipoles on phonon coordinate displacement) contributions to the one-particle transition dipoles. It is argued that our findings for anthracene should prove useful for triplet exciton bands in other organic solids.     

Dependence of impurity zero-phonon band thermal broadening and shift on impurity site and vibron level in organic crystals

Experimental results on the thermal broadening and shifts of impurity zero-phonon bands in some organic mixed crystals are reported and interpreted in terms of the electron-phonon interaction. Attention is focused on the variation of the thermal broadening and line shift parameters with (1) impurity site in a system exhibiting several energetically different impurity sites and with (2) the vibron level in a given final electronic state of the impurity. Experiments were conducted over a temperature range which ensures that hot vibron transitions are negligible. Data from the 5600 A ¹B₁ ← ¹A₁ transition of 2-phenyl-l-monoazaazulene in p-terphenyl show that the variations of the above parameters with impurity site are as large as the variations of the same between different chemical systems. No dependence of the thermal broadening parameters on the impurity vibron level is observed for the above system or the 7000 A ¹B₁ ← ¹A₁ transition of azulene in naphthalene. It is shown that, within the adiabatic (electron-nucleus) and harmonic approximations, the zero-phonon band spectral shape function arising from the electron-phonon interaction should be independent of the final vibron level of the impurity transition.     

Valence transitions of Br2 in Ar matrices: interaction with the lattice and predissociation

Fluorescence spectra from v(')=0 of the B, A and A(') states of Br(2)Ar are presented for excitation wavelengths from 630 to 540 nm with high resolution, to evaluate isotopic splittings in emission and absorption. The observed progression of sharp zero phonon lines (ZPLs) from v(')=2 to v(')=19 in B excitation is used to derive spectroscopic constants. The ZPL broadening and the growing phonon sideband (PSB) contributions indicate an increase of matrix influence on the X-B transition with rising v('). Contributions of the PSB are parameterized with the Huang-Rhys coupling constant S, where S=1 near the potential minimum reflects the electron-phonon coupling and S=4 close to Franck-Condon maximum originates from vibrational coupling. The PSB spectral composition correlates with the matrix phonon density of states, and the ZPL broadens and shifts with temperature. Two crossings with repulsive states (between v(')=4-5 and v(')=7-9) leading to matrix induced predissociation and a third tentative one between v(')=14 and 15 are indicated by ZPL broadening, population flow, and spectral shifts. The crossing energies are close to gas phase and matrix calculations. The stepwise flow of intensity from B via repulsive states to A(') and, similarly, from the A continuum to A(') is discussed. Emission quantum efficiency of the B state decreases from near unity at v(')=0 to less than 10(-3) at v(')=19. Broadening of ZPL near crossings yields predissociation times of 5 and 2.5 ps corresponding to probabilities of 5% and 10% per round-trip for the two lowest crossings, respectively.