Method of describing highly excited vibrational-rotational states of diatomic molecules

Institute of Applied Physics, Academy of Sciences of the USSR. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 33, No. 3, pp. 281–289, March, 1990.     

Collisions of low-energy electrons with carbonyl-containing molecules in a gas phase

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 6, pp. 135–139, November–December, 1995.     

Dissociative attachment of electrons to excited molecules

The development and the first results from an experiment to carry out dissociative attachment to excited molecules are discussed. A brief summary of the relevance and status of such measurements are given. Apart from measuring the absolute cross sections from excited and state selected SO₂ molecule, we have been able to characterize the negative ion resonances using the excited state dissociative attachment. In addition, the state specificity of the electron attachment process has been used to derive information on the excited neutral state itself which has not been possible using optical spectroscopy. The applicability of this technique to other species are also discussed.     

Inelastic collisions between excitons in semiconductors—I: Collisions with excited final states

The exciton-exciton (Exc-Exc) inelastic collision cross sections for the different semiconductors CdS, ZnO, CdSe, Si and Cu₂O have been calculated in the Born approximation. The simple transitions Exc (1s/B) + Exc (1s/A)→ Exc (1s/B) + Exc (nl /A) where nl = 2s, 2p, 3s, 3p and 3d have been The calculations are carried out as functions of the different available values of σ = m¹_e/m¹_h where m¹ and m¹_h are, respectively, the electron and the hole effective masses for the corresponding semiconductors.     

Formation of excited cesium ions in collisions of electrons with cesium iodide molecules

The process of formation of excited Cs ions in simple collisions of electrons with CsI molecules was investigated by the method of extended intersecting beams. Excitation cross sections measured for CsII spectral lines were used in the calculation of cross sections for excitation of energy levels. The contribution of cascade transitions to the total cross section for excitation of an energy level was determined for certain levels. Possible ways of formation of Cs^+* at low energies of the electrons are discussed. Moscow Power Engineering Institute, 14, Krasnokazarmennaya Str., E-250, Moscow, 111250, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 316–322, May–June, 1999.     

Dissociative attachment of low-energy electrons to vibrationally excited hydrogen molecules

Dissociative electron attachment to hot hydrogen molecules is studied in the framework of nonlocal resonance model. The method based on the use of the Bateman approximation, well known in nuclear physics, is adapted for solving the Lippmann-Schwinger integral equation of the nonlocal resonance model and applied to the calculation of cross sections of inelastic resonant electron-molecule collisions. The proposed method is compared with the Schwinger-Lanczos algorithm used extensively for the treatment of these processes. It is shown that the Bateman approximation is very useful and efficient for treating the non-separable nonlocal potentials appearing in the integral kernels of the nonlocal resonance models. The calculated cross sections for the dissociative attachment of electrons to vibrationally excited hydrogen molecules are of importance for astrophysics. This paper is dedicated to Prof. J. Bičák on the occasion of his 60th birthday.     

Collisions of fast electrons with positronium atoms

Summary Elastic and inelastic collisions of fast non-relativistic electrons with positronium atoms have been studies in the Born-Ochkur approximation. It has been shown that exchange plays an important role for transitions between states with the same parity as in this case the direct scattering amplitude vanishes. Numerical results for the total and ortho-para conversion cross-sections for the 1s→1s, 1s→2s and 1s→2p transitions have been presented for projectile energies varying from 0.1 to 10 keV. According to charge symmetry, presented results apply also to positron projectiles.     

Broadening and shifting of vibrational-rotational lines corresponding to the highly excited rotational states of the water molecule

Self-pressure-induced, as well as argon- and nitrogen-induced, broadening γ and shifting δ coefficients of vibrational-rotational lines of the water molecule have been calculated. The asymptotic behavior of the coefficients γ and δ at J → 42 and K _a → J has been studied. For the calculation of the parameters γ and δ, we used the wave functions obtained from the analysis of highly excited rotational states of the H₂O molecule with the maximal ever observed values of rotational quantum numbers J _max = 42, K _amax = 32. Rotational states were analyzed in the method of effective Hamiltonians using generating functions for the first eight vibrational states of the molecule.     

Formation of excited singly charged barium ions in collisions of slow electrons with barium dibromide molecules

The method of extended crossing beams is used to study inelastic collisions of slow electrons with barium dibromide molecules. The resulting optical emission spectrum contains only the spectral lines of the singly charged barium ion. At an exciting electron energy of 100 eV, the cross sections of dissociative excitation for nine spectral lines of BaII are measured; for all these lines, the optical excitation functions over an electron energy range of 0 to 100 eV are recorded. The possible channels of the dissociative excitation of BaII are discussed.     

Extension of the Local Approach to excited states of molecules

The Local Approach for the calculation of electronic correlation energies in molecules is generalized to excited states. Within the Local Approach correlated states are obtained by applying a local projection operator on the Hartree-Fock ground state or simple reference states, which are used as zeroth order approximations for the excited states, respectively. In the case of excited states one has in addition to require the correlated states to be orthogonal on the states lower in energy. This is done by using Schmidt's orthogonalization. The method is applied to a simple model of the H₆-ring for which an exact solution is available. The results obtained are of comparable quality as for the ground state.     

Dynamic fluorescence quenching and the highest excited states of molecules

The dynamic fluorescence quenching in organic molecules, or quenching of the second kind according to Vavilov’s classification, is an efficient method of investigating excited states in solutions and is widely used in various fields. The effect of quenching on the intensity of the fluorescence from the first and higher singlet states of organic molecules is studied. The results may serve as a basis for determining the nature of the short-wavelength luminescence and can be used to distinguish the S _n fluorescence from the comparably intense luminescence of impurities, which is a very important problem when investigating such emissions. A method for obtaining dynamic quenching by specially chosen quenchers is proposed. The method is based on an experimentally found strong increase in the constants of bimolecular collisions of luminophore and quencher molecules when the luminophore is excited through the highest singlet states.     

Collisional and radiative processes with participation of highly excited states of atoms and molecules

A number of processes in which highly excited states of atoms and molecules participate are investigated. These processes are of interest for the kinetics of a low-temperature plasma, for atomic and molecular spectroscopy, and for astrophysics. A quasiclassical theory is developed for transitions between Rydberg states with change of the principal quantum number, and also for the processes of direct and associative ionization of highly excited atoms, which result from collisions between a neutral particle and its atomic core. The state of the inner electrons of a quasimolecular (molecular) ion is not altered by transitions of the outer electrons. Specific calculations are carried out for the case of the collision of hydrogen H(n) with helium He (1s²) atoms. It is shown that the cross sections and the rate constants of these processes are determined in this case by the mechanism investigated in the paper, and not by scattering of the Rydberg electron by the neutral particle. The cross sections for dipole excitation and dissociation of molecular ions from high vibrational energy levels by electron impact is calculated in the Born-Coulomb approximation. The cross sections and the rates of dissociative and three-particle attachment of electrons to ions are determined. The processes of autoionization and autodissociation decay of Rydberg states of vibrationally excited molecules are determined. Also investigated are radiative transitions near the dissociation limit of diatomic molecular ions and neutral molecules, viz., photodissociation and radiative decay of high vibrational levels, and photodissociation and translational (inverse-bremsstrahlung) absorption in collision of atomic particles.Translated from Trudy Ordena Lenina Fizicheskogo Instituta im. P. Lebedeva AN SSSR, Vol. 145, pp. 80–130, 1984.     

Resonance-Raman-induced Kerr effect in molecules in the ground and electronically excited states

A theoretical investigation of the resonantly enhanced, Raman-induced Kerr effect (resonance-RIKE) is given, taking into account the resonance absorption of the laser wave and the population of excited electronic states. Line shape, maximum amplification and optimum conditions for the resonance-RIKE from the ground state as well as for the resonance-RIKE from an initial excited electronic state are discussed in detail. The possibility is studied of applying this method to the investigation of the vibrational structure of excited electronic states in molecules.     

Dissociative attachment of low-energy electrons to vibrationally excited molecules using a photoelectron source

The process of dissociative attachment (DA) of low-energy electrons ) to vibrationally excited sodium dimer molecules is studied with high electron energy resolution () in a supersonic molecular beam. A novel photoelectron source, based on two-step photoionization of the sodium atoms in the beam, may deliver a current of up to 1 nA and has been used with a current of typically 0.2 nA in this experiment. The energy dependence of the rate of sodium anion formation is determined by ion detection based on a time-of-flight analysis. The molecules are selectively excited to levels using the technique of coherent population transfer by delayed pulses (STIRAP). The comparison of the experimental data with recent resonance model calculations based on improved potential curves reveals generally good agreement for levels v ”>12. For some distinct differences between theoretical and experimental results persist. Received: 21 November 1998 / Received in final form: 7 April 1999