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.     

Kinematic and electrooptical anharmonicity in the semiempirical intensity theory of IR and raman spectra of polyatomic molecules

Saratov State University, 83 Astrakhanskaya Str., Saratov, 410601, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 6, pp. 49–57, November–December, 1995.     

Extreme narrowing of bands in the fluorescence excitation spectra of organic molecules in solid solutions

Extreme narrowing of bands in the fluorescence excitation spectra of some organic molecules is found. This narrowing is observed when the excitation spectrum of a narrow spectral interval of the fluorescence band is recorded. The effect is observed in a wide variety of matrices and permits one to determine exactly the vibronic structure of the excited electronic state of the dissolved molecule.     

Theory of polarized fluorescence of polyatomic radicals upon photodissociation of complex molecules in the gas phase

The effect of rotational predissociation on the polarization response of an ensemble of photofragments is investigated within the framework of the model with free scatter of fragments for the most general case when both original molecules and fragments are asymmetric rotators. Photoinduced decomposition reactions with single- and two-photon excitation of fragment fluorescence are analyzed. Second- and third-order orientational correlation functions determining the polarization degree of fragment fluorescence are calculated. The behavior of these correlation functions depending on the shape of original molecules and fragments, directions of dipole moments, and characteristic times of the process are analyzed. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 908–914, November–December, 1998.     

The width of the rotational contour of vibrational and vibronic bands of complex molecules in the gas phase as a temperature indicator

From the independence of the contour of spectral density of the rotational (orientation) correlation function of a rigid molecular top of arbitrary symmetry on temperature in the frequency scale based on the reduced time of rotational orientation relaxation and from the near independence of the rotational contour of vibrational and vibronic absorption bands of dipole transitions in the same coordinates in a model of “regular diffusion” of the transition oscillator with a classically rotating rigid molecular top, it is suggested that it is possible to use the halfwidth of the contour for estimation of temperatures. Data are presented on the halfwidth of 48 contours of bands of A, B, and C types at this frequency for 12 compounds for a temperature range of from units to 500 degrees of absolute temperature measured experimentally and (for low temperatures) calculated by the quantum theory. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 312–317, May–June, 1997.     

2S-excitation of atomic hydrogen by electrons at intermediate energies

The method of Das developed recently to analyse elastic scattering of electrons by atoms has been extended in the present paper to inelastic scatterings. The method has been applied for the computation of 2S-excitation, cross-sections at two typical intermediate energiesviz. 54.4 eV and 100 eV energies. Some of the results are compared with available experimental results and are found to be in satisfactory agreement with these.     

Collisional depolarization of fluorescence of polyatomic molecules in the gas phase by excited state quenchers

A new method of extracting information on the efficiencies of quenching of an excited state and collisional reorientation from the data on the fluorescence depolarization of molecular vapors by quenchers of the excited state is proposed. The method does not involve collisional cross sections and fluorescence lifetimes. From the experimental data on the depolarization of polarized luminescence of para-quaterphenyl and 2-(4′-dimethylamine) phenyl-5-phenyloxydiazole by oxygen and nitrogen, the ratios of the constants of the excitedstate quenching and orientation randomization (fluorescence depolarization) by oxygen are obtained. For these molecules, the probabilities of the excited-state quenching q and orientation randomization s per collision with oxygen molecules are determined (q=0.25±0.04 and s=0.13±0.04 for para-quaterphenyl and q=0.2±0.04 and s=0.21±0.04 for 2-(4′-dimethylamine)phenyl-5-phenyloxydiazole). The self-quenching of fluorescence of perylene vapors, with the probability 0.28 per collision, is found.