Restoration of selection rules in nonadiabatic resonant inelastic x-ray scattering

Recently a new effect in the Raman scattering of x-ray radiation has been predicted theoretically and discovered in experiments, the effect of restoration of the selection rules for the scattering tensor under strong electron-vibrational interaction. We propose a fairly simple model for describing this effect, a model that allows for an exact solution and takes into account the real vibrational structure of the molecule and electron-vibrational interaction. Zh. éksp. Teor. Fiz. 112, 37–49 (July 1997)     

Measurements of core hole localization in x-ray Raman scattering

The problem of core hole localization in symmetrical systems is a fundamental problem of x-ray spectroscopy and concerns some basic aspects of quantum theory. Recent theoretical as well as experimental investigations of resonant x-ray Raman scattering indicate that the solution to this problem depends on the measurement. In the present work we propose an experimental scheme which allows a direct measurement of the atom to which the core hole is localized. The idea behind the proposal is based on the electron Doppler effect and the photoelectron-photoion coincidence technique. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 12, 1005–1008 (25 June 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Orientation of stereoisomers by electromagnetic field

A magnetic orientation is shown to appear during light-induced drift of stereoisomers relative to a buffer gas. The magnetic orientation can be initiated even by linearly polarized or nonpolarized radiation.     

Nuclear dynamics in X-ray Raman scattering

Accepted: 6 March 1997     

Raman Scattering at Resonant or Near-Resonant Conditions: A Generalized Short-Time Approximation

We investigate the dynamics of resonant Raman scattering in the course of the frequency de-tuning. The dephasing in the time domain makes the scattering fast when the photon energy is tuned from the absorption resonance. This makes frequency detuning to act as a cam-era shutter with a regulated scattering duration and provides a practical tool of controlling the scattering time in ordinary stationary measurements. The theory is applied to resonant Raman spectra of a couple of few-mode model systems and to trans-1,3,5-hexatriene and guanine-cytosine (G-C) Watson-Crick base pairs (DNA) molecules. Besides some particular physical effects, the regime of fast scattering leads to a simplification of the spectrum as well as to the scattering theory itself. Strong overtones appear in the Raman spectra when the photon frequency is tuned in the resonant region, while in the mode of fast scattering, the overtones are gradually quenched when the photon frequency is tuned more than one vibra-tional quantum below the first absorption resonance. The detuning from the resonant region thus leads to a strong purification of the Raman spectrum from the contamination by higher overtones and soft modes and purifies the spectrum also in terms of avoidance of dissociationand interfering fluorescence decay of the resonant state. This makes frequency detuning a very useful practical tool in the analysis of the resonant Raman spectra of complex systems and considerably improves the prospects for using the Raman effect for detection of foreign substances at ultra-low concentrations.     

Gas diffusion induced by resonance light field

The physical interpretation of a light-induced gas diffusion phenomenon is given and the experimental observation of this phenomenon in Na vapors is reported. It is established that Na vapors resonantly interacting with radiation can move along or against the direction of light propagation due to collisions with a buffer gas.     

Optical limiting and pulse reshaping of picosecond pulse trains by fullerene C60

We present a dynamical theory of nonlinear absorption and propagation of a laser pulse train that contains 20 subpulses with an individual pulse width of 100 ps. It is shown that the accumulative nonlinearity and the reverse saturation absorption play important roles in the optical limiting performance and pulse shaping. When the incident field is not too strong, the population transfer reveals a slow response process, and the periodic sequence of short light pulses can be regarded as a continuous long pulse. The general theory is applied to fullerence C₆₀, which is a popular reverse saturable absorption material and a good limiter because of its larger excited-state absorption cross-section compared with that of the ground state. The propagation of the front subpulses is mainly affected by the linear transition between the ground state and the first excited singlet state, while the latter subpulses are attenuated by the excited-state absorption. Moreover, these two different kinds of absorption mechanisms result in different radial distributions for different subpulses. The pulse propagation is studied by solving numerically the coupled rate equations and the propagation equation of the optical pulse intensity, using experimental parameters as input. We suggest a new method to measure the lifetime of the triplet state.     

Simulations of resonant X-ray emission spectra of molecules

ab initio calculations. We let each molecule, or group of molecules, represent one particular aspect: calculations on molecular oxygen, benzene, carbon dioxide, aniline, fullerenes, chlorofluoromethanes, carbon monoxide, and polyenes are used to illustrate, in order, the effects of parity selection rules and core hole localization, vibronic coupling and symmetry breaking, frequency dependence of symmetry breaking, the role of chemical shifts, the character of band gap excited spectra, polarization anisotropies, the role of screening, and the role of excitons. Accepted: 6 March 1997     

High resolution X-ray photoelectron spectroscopy on nitrogen molecules

This paper summarizes recent developments for experimental and theoretical studies on core-level photoelectron spectroscopy of N₂. Analysis of experimental spectra reveals that the 1σ_g and 1σ_u core-hole states differ in energy by ~100meV and in equilibrium bond length by ~0.04pm, in agreement with ab initio predictions. The ratio of the 1σ_g and 1σ_u photoionization cross sections measured in the photon energy range up to 1 keV reveals oscillatory structure due to two-center interference, equivalent to Young’s double-slit experiment, as Cohen and Fano predicted. The experimental Auger rates for the transition to the dicationic ground state are found to be different by a factor of two for 1σ_g and 1σ_u hole states and are well reproduced by the ab initio calculations. All these findings support the delocalized picture of the core hole. Discussion is given how many-body processes involved and observations for these processes affect the observation of the localized and/or delocalized core hole.     

Polarisation of a dipolar gas by drift

Linear molecules without a center of symmetry are shown to be oriented during their drift with respect to a buffer gas.