Defects in silicon: the role of vibrational entropy

Vibrational free energies are calculated from first-principles in the same Si periodic supercells routinely used to perform defect calculations. The specific heat, vibrational entropy, and zero-point energy obtained in defect-free cells are very close to the measured values. The importance of the vibrational part of the free energy is studied in the case of two defect problems: the relative energies of the H₂ and H₂^∗ dimers and the binding energy of a copper pair. In both cases, the vibrational entropy term causes total energy differences to change by about 0.2 eV between 0 and 800 K. We also comment on the rotational entropy in the case of H₂ and the configurational entropy in the case of the Cu pair. These examples illustrate the importance of extending first-principles calculations of defects in semiconductors to include free energy contributions.     

Quantum ergodicity and energy flow in molecules

We review a theory for coupled many-nonlinear oscillator systems that describes quantum ergodicity and energy flow in molecules. The theory exploits the isomorphism between quantum energy flow in Fock space, that is, vibrational state space, and single-particle quantum transport in disordered solid-state systems. The quantum ergodicity transition in molecules is thereby analogous to the Anderson transition in disordered solids. The theory reviewed here, local random matrix theory (LRMT), describes the nature of the quantum ergodicity transition, statistical properties of vibrational eigenstates, and quantum energy flow through the vibrational states of molecules. Predictions of LRMT have been observed in computational studies of coupled nonlinear oscillator systems, which are summarized here. We also review applications of LRMT to molecular spectroscopy and chemical reaction rate theory, including adoption of LRMT in theories that predict rates of conformational change of molecules taking place at energies corresponding to those below and above the quantum ergodicity transition. A number of specific examples are reviewed, including the application of LRMT to predict (1) dilution factors of IR spectra of organic molecules, (2) rates of conformational change in chemical and photochemical reactions, (3) conformational dynamics of biological molecules in molecular beams, (4) rates of hydrogen bond breaking and rearrangement in clusters of biological molecules and water, and (5) excited state proton transfer reactions in proteins.     

Extended modes and energy dynamics in two-dimensional lattices with correlated disorder

We study the nature of the vibrational modes in a two-dimensional harmonic lattice with long-range correlated random masses, with power-law spectral density S(k)∼1/k^α. We obtain numerically the scale invariance of the fluctuations of the relative participation number and the local density of states. We find signatures of extended vibrational modes when α>α_c and α_c depends on the magnitude of disorder. In order to confirm this claim, we also study the time evolution of an initially localized perturbation of the lattice. We show that the second moment of the spatial distribution of the energy displays a ballistic regime when α>α_c, in agreement with the occurrence of extended vibrational modes.     

Influence of intramolecular vibrations in charge redistribution at the pentacene-graphite interface

We have investigated the relation between the intramolecular vibrational modes of pentacene and the charge redistribution at the pentacene-graphite interface by using high-resolution electron-energy-loss-spectroscopy. The three main vibrational peaks shift to lower energies as the pentacene film thickness decreases. In order to discuss this energy shift, we have calculated the vibrational energies of a free pentacene molecule by changing its charge state. We have also calculated the vibrational energies of a pentacene molecule adsorbed on a graphite sheet by changing the pentacene-graphite distance. Taking the experimental and calculation results into account, we conclude that the observed energy shifts result from an intramolecular charge redistribution. The present results indicate that the effect of an intramolecular charge redistribution is essential to discuss the origin of an energy shift observed in a vibrational study of an organic molecule/substrate interface.     

Temperature and size dependence of the optical response of small Ag clusters

The absorption spectra of small Ag ⁺ n clusters are calculated at finite vibrational temperature by using a microscopic tight-binding RPA method. We consider free clusters with sizes between n = 3 and n =13 and take into account explicitly the degrees of freedom corresponding to the 4 d-electrons. We analyze the optical absorption as a function of the cluster size. We show that the contribution of the d-electrons has an important influence on the size dependence of the energy of the Mie plasmon. We also perform ensemble averages to obtain the absorption spectra for different vibrational temperatures. We obtain relatively good agreement with experiment for a temperature . The dynamics of the 4 d-electrons, which shows in small clusters an incipient delocalized character for n >7, yields an important contribution to the absorption spectrum already for n =13. We find that the strength of this contribution can be controlled by varying the vibrational temperature. Received: 4 January 1999 / Received in final form: 12 May 1999     

Local field corrections for light absorption by fullerenes

Semi-empirical atom-atom potential energy calculations based on pairwise additive interactions are performed and, after applying the Born-Oppenheimer approximation to separate high frequency vibrational modes from low frequency orientational and translational modes, the infrared vibrational spectra of CO₂ and N₂O monomers trapped in an argon matrix at a temperature of 5 K are determined. It is shown that only a double substitutional site in argon can accommodate N₂O, whereas CO₂ is trapped in two distinct sites, of single and double substitutional types. The model shows that splitting of the degenerate mode occurs for both molecules in the double site. In the ground electronic state, the vibrational frequency shifts due to the matrix and the vibrational transition moments for low-lying levels are determined using the contact transformation method, as used for gas phase calculations. Calculated energy levels compare well with observed ones and the theory also predicts some unobserved levels. Moreover, calculations show no significant changes in the dipole moments of both CO₂ and N₂O trapped molecules. Received 22 March 2000 and Received in final form 10 May 2000     

Dissociation Energies of Diatomic Molecules

Molecular dissociation energies of 10 electronic states of alkali molecules of KH, ^7LiD, ^7 LiH, ^6LiH, NaK, NaLi and NaRb are studied using the highest three accurate vibrational energies of each electronic state, and an improved parameter-free analytical formula which is obtained starting from the LeRoy Bernstein vibrational energy expression near the dissociation limit. The results show that as long as the highest three vibrational energies are accurate, the current analytical formula will give accurate theoretical dissociation energies De^theory, which are in excellent agreement with the experimental dissociation energies De^expt.     

Local bond breaking via STM-induced excitations: the role of temperature

We discuss the influence of temperature on local bond breaking through multiple vibrational excitations induced by inelastic tunneling in the STM. We focus on hydrogen desorption from the H---Si(111) and H---Si(100) systems, but the results are general. The substrate temperature affects the desorption yield in two important ways: first, lowering the temperature increases the H---Si vibrational energy relaxation time, resulting in a higher effective adsorbate temperature and an increased desorption yield. Second, lowering the substrate temperature decreases the dephasing rate of the H---Si modes (manifested by a decrease of the infrared absorption linewidth), which then reduces the rate of incoherent (Förster) vibrational energy transfer away from the Stark-shifted H---Si mode under the tip. This increases the localization of the vibrational energy and enhances the probability for multiple vibrational excitation and desorption. Finally, we discuss the possible implications of our findings on the mechanism of MOS device degradation by hot electrons.     

Breather trapping and breather transmission in a DNA model with an interface

We study the dynamics of moving discrete breathers in an interfaced piecewise DNA molecule. This is a DNA chain in which all the base pairs are identical and there exists an interface such that the base pairs dipole moments at each side are oriented in opposite directions. The Hamiltonian of the Peyrard-Bishop model is augmented with a term that includes the dipole-dipole coupling between base pairs. Numerical simulations show the existence of two dynamical regimes. If the translational kinetic energy of a moving breather launched towards the interface is below a critical value, it is trapped in a region around the interface collecting vibrational energy. For an energy larger than the critical value, the breather is transmitted and continues travelling along the double strand with lower velocity. Reflection phenomena never occur. The same study has been carried out when a single dipole is oriented in opposite direction to the other ones. When moving breathers collide with the single inverted dipole, the same effects appear. These results emphasize the importance of this simple type of local inhomogeneity as it creates a mechanism for the trapping of energy. Finally, the simulations show that, under favorable conditions, several launched moving breathers can be trapped successively at the interface region producing an accumulation of vibrational energy. Moreover, an additional colliding moving breather can produce a saturation of energy and a moving breather with all the accumulated energy is transmitted to the chain.     

Ultrafast multidimensional dynamics of strong hydrogen bonds

The laser driven dynamics of the OH(D) stretching vibration in phthalic acid monomethylester is investigated. The combination of a 55-dimensional all-Cartesian reaction surface Hamiltonian and the time-dependent self-consistent field approach is shown to provide a microscopic picture of intramolecular vibrational energy redistribution taking place upon interaction with an external laser field. Choosing suitable zeroth-order vibrational states and combinations thereof a quasi-periodic in-phase and out-of-phase oscillatory behavior is observed manifesting energy flow on different time scales. The fingerprints of this behavior in transient absorption spectroscopy are also discussed. Received 24 August 2000 and Received in final form 11 October 2000     

Temperature-dependent photoreflectance of SnS crystals

The optical properties of single-crystal SnS were studied by photoreflectance (PR) spectroscopy. Temperature-dependent PR spectra were measured in the range 20–200 K. A room-temperature bandgap energy value of E_g=1.317 eV was estimated by fitting the temperature dependence of the bandgap energy obtained from the PR spectra. The vibrational properties of orthorhombic SnS were studied using Raman spectroscopy. Four vibrational modes were detected at 95, 163, 191, and 218 cm^–1.     

Effects of solvation on dissociative electron attachment to methyl iodide clusters

Using laser photoelectron attachment to methyl iodide clusters in a differentially-pumped seeded supersonic helium beam and mass spectrometric ion detection, we have measured the rate coefficients for formation of (q = 0-2) ions over the electron energy range 0-100 meV with an effective energy width of about 2.5 meV. Whereas a prominent vibrational Feshbach resonance just below the onset for the C-I stretch vibration ( ) is observed for dissociative attachment to monomers (yielding I^- ions), only weak and broad structure, shifted to lower energies, is detected for formation of ions and essentially no structure is left in the attachment spectrum for . These observations are interpreted by model R-matrix calculations which successfully describe the DA cross-section for the monomer and qualitatively recover the trend observed for cluster ion formation. For the clusters, the effects of increased electron-target long-range interaction and of solvation as well as coupling to soft vibrational modes lead to strong broadening and shifting of the vibrational Feshbach resonance and, ultimately, to its disappearance. Received 29 November 1999 and Received in final form 14 January 2000     

Hydrodynamics of resonance oscillations of columns of inelastic particles

We study oscillations of a one-dimensional (1D) column of N slightly inelastic particles, produced by a piston vibrating at one end of a closed tube. It is found that for large enough vibrational amplitudes of the piston, the column oscillates periodically with the period equal to the vibrational period. The oscillation patterns are governed by the shock waves propagating across the column. The averaged kinetic energy per particle is shown to be proportional to the square of the vibrational frequency, omega. This energy also strongly depends on the vibrational amplitude. The maximal value of this kinetic energy achievable by these external vibrations is found to be of order omega(2)L(2), where L is the total volume (length) of the tube free of particles. The above results on the column resonance oscillations are also predicted by a 3D hydrodynamic model of an inelastic granular gas.     

A comparative study of the vibrational spectra of OCS and HCP using the Lie algebraic method

Using the Lie algebraic method the vibrational energy levels of OCS and HCP are calculated for 58 vibrational bands each using the local Hamiltonian. A comparative study is made between the two.     

Nonlinear electron-lattice interaction on excited states in polythiophene

In consideration of the effects of the square term of the electron-lattice interaction and the bond-bending term, the energy spectra and the localized vibrational modes around a bipolaron of the polythiophene are investigated based on the one-dimensional and two-dimensional extension SSH model. The results show that, with the influence of the square term, the energy gap increases, the frequencies of all the localized vibrational modes around a bipolaron decrease and their localizations also shift. It is noted that, an even-parity mode has been found which corresponds to absorption peak at 1220 cm⁻¹. When the bond-bending term is considered, the frequencies of the localized modes increase and five new localized modes appear. Among them, one Raman active mode and three infrared active modes may correspond the observed RRS absorption peaks at 1047 cm⁻¹ and three infrared absorption peaks at 370, 1020, 1120 cm⁻¹ in the experiments.     

Measurement of vibrational energy flow in a plate with high energy flow boundary crossing using electronic speckle pattern interferometry

The measurement of vibrational energy flow is an important tool in understanding the vibrational behaviour of structures. In the past, because of transducer constraints, the measurement of vibrational energy flow was mostly restricted to single point measurements. However, recent developments in advanced laser measurement techniques, such as electronic speckle pattern interferometry (ESPI), have gained interest in applying two-dimensional, multi-point measurement techniques to the estimation of vibrational energy flow. This paper addresses the measurement of vibrational energy flow in a plate by using an ESPI based vibrational energy flow measurement technique. A radially symmetric bending wave plate vibration model is introduced and theoretical expressions for energy-based quantities are derived. To assess the accuracy of the measurement method, these theoretical quantities are compared to synthetic results derived from the ESPI energy flow measurement technique. The ESPI measurement technique is also applied to an experimental ‘infinite’ plate. Thus, a specially designed experimental apparatus was constructed so as to minimise undesired wave reflections in the plate and, thus, achieve a high energy flow boundary crossing at the edges of the plate. To reduce the effect of optical noise contamination on the ESPI measured out-of-plane plate displacement data, optimal filters were applied prior to the vibrational energy flow computation. To appraise the accuracy of the experimental method, measured vibrational power on the plate is compared with measured vibrational input power. A difference of less than 1 dB between both quantities indicates that vibrational energy flow within a rectangular plate that contains radially symmetric wave propagation can be measured to a good degree of accuracy if appropriate filtering is applied.     

Probing solvation dynamics with femtosecond vibrational spectroscopy

We explain why solvent reorganization can induce both red- and blue-shifting of vibrational transitions of a particular probe molecule upon excitation to the S₁ electronic state. We observe with femtosecond vibrational spectroscopy, after hydrogen-bond cleavage dynamics, an additional blue shift of the carbonyl stretch of coumarin 102 of 7 cm^-1 when dissolved in chloroform. Received: 28 June 2000 / Published online: 7 August 2000     

Finite-temperature thermophysical properties of fcc-Ca

At an extreme environment, such as high-temperature and high-pressure, harmonic theory has obvious limitations, where the anharmonic effects are influential in determining bulk properties of the materials. In this regard, necessity for incorporating anharmonicity through vibrational contribution and thermally excited electrons to the total free energy at finite temperatures is illustrated taking an example of divalent fcc-Ca. In this regard, we have employed a coupling scheme of combining recently proposed mean-field potential (MFP) with the local pseudopotential to obtain vibrational contribution to the total free energy. To access the applicability of the present coupling scheme, we have calculated temperature variation of several thermodynamical properties. Static EOS, shock Hugoniot and temperature along principal Hugoniot are also estimated. Results are satisfactorily compared with the other theoretical and experimental data and the use of local pseudopotential in conjunction with the MFP approach is justified.     

Local modes of silane within the framework of stretching vibrational polyads

We define stretching relative equilibria (RE) of silane and other similar tetrahedral molecules in terms of the dynamical polyad symmetry which assumes the resonance condition 1:1 between the two stretching vibrational modes ν₁ and ν₃ of the molecule. Exploiting symmetry and topology arguments and reducing the dimension of the classical mechanical system, we find these RE. One of them, with local symmetry C_3v and minimal energy within a polyad, corresponds to the local modes. We give the upper energy limit of the local mode localization within a polyad.     

Reaction dynamics of Cl O ClO O

Applying the two photon laser induced fluorescence technique for nascent state resolved ClO() detection, the reaction dynamics of Cl+O ClO+O₂ is investigated. The ClO product is formed in its electronic ground state ClO(). A complete product state analysis in terms of vibration, rotation, spin-orbit and -states indicates that nascent ClO radicals are formed in v =0-6 vibrational states peaking at v =3. The ClO fragment shows a moderate rotational excitation, described by a Boltzmann distribution with a temperature parameter of 1300 K 200 K. The spin orbit ratio of :. Most of the excess energy is released as translational energy or as internal energy of the O₂ product. By comparing our results with the trajectory studies of Farantos and Murrell, we favour a reaction mechanism, where the transition complex is planar containing an essentially linear OOCl group. In order to determine the possible influence of vibrationally excited ClO on other trace components of the atmosphere, especially the reaction ClO(v >0)+ O₃, a rough estimate of the vibrational relaxation rate of ClO with the major atmospheric collision partner, N₂, has been performed. A measurement of the vibrational distribution of ClO at different N₂ pressures indicates a mean vibrational relaxation rate of . Received: 27 February 1998 / Revised: 1st April 1998 / Accepted: 15 April 1998