Polarizability of molecules on their vibrational excitation

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 53, No. 5, pp. 793–800, November, 1990.     

Intermolecular vibrational relaxation upon multiphoton excitation of triplet molecules by a CO2 laser

Intermolecular vibrational relaxation is studied in mixtures of polyatomic molecules (benzophenone and fluorene) with bath gases after multiphoton excitation of the triplet molecules by CO₂ laser radiation. The dependences of the decay rate and the intensity of laser-induced delayed fluorescence on the laser energy density E _CO2 and pressure P _fg of bath gases are analyzed. They are found to be different for the fast and slow components of delayed fluorescence, which decays nonexponentially. It is shown that a change in the decay rate of the fast fluorescence component with increasing pressure P _fg is governed by the properties of vibration-translation relaxation. The efficiency β of this process is estimated in a broad range of vibrational energies. It is found that β weakly changes with increasing E _vib upon excitation of molecules to high vibrational levels. The features of intermolecular vibrational relaxation at high densities of anharmonically coupled vibrational states are discussed.     

Threshold vibrational excitation of CO2 by slow electrons

Threshold structures, reminiscent of those seen in the polar hydrogen halides, have recently been observed in the cross sections for electron impact excitation of certain vibrational levels of the nonpolar CO2 molecule. These structures occur at energies outside the range where shape resonances dominate the dynamics. We propose a virtual state model that describes the multidimensional nuclear dynamics during the collision and explains quantitatively the selectivity observed in the excitation of the Fermi dyad, as well as the pattern of threshold peaks and oscillations seen in the upper levels of the higher polyads.     

Rotational and vibrational excitation of sputtered diatomic molecules

The rotational and vibrational level population distributions of ground and electronically excited states of several homonuclear and heteronuclear molecules are calculated for direct ejection, association, and associative ionization mechanisms of molecule sputtering. The cascade properties, formation mechanism, initial atom separation, and axis orientation to the surface are clearly reflected in the sputtered molecule distributions. In general, extensive non-Boltzmann rotational and vibrational distributions are predicted. The probability that an atom pair survives the ejection, for typical sputtering parameters, is high; approximately 50% for homonuclear molecules to near 100% for hydrides. The predictions are compared with experimental optical emission spectra in the accompanying paper.     

Role of weak transitions in multiphoton excitation of molecules by IR laser radiation

Simultaneous excitation of a considerable part of molecules from many rotational levels of the ground state to higher vibrational states by IR laser radiation can be explained by considering weak transitions in a rotational band structure as it is shown at the example of SF₆ molecule. Very accurate compensation of anharmonicity in relatively wide spectral interval at comparatively low intensity of laser radiation can be explained on this basis. The considered scheme can be applied to the molecules of various symmetry with arbitrary anharmonicity.     

Population inversion on vibrational transitions of molecules under nonresonant optical excitation

The possibility of obtaining a population inversion on vibrational transitions of molecules through nonlinear effects when the pump radiation is absorbed in the wings of spectral lines is investigated theoretically. We show that a population inversion can be produced in molecules on vibrational transitions when intense pump radiation is absorbed in the blue wing of the R branch of the vibrational-rotational molecular spectrum. This effect is related to inequality of the probabilities of the absorption and stimulated emission of radiation and is attributable to collisional transitions between rotational levels. We have ascertained that the larger the rotational constant of the molecule and the higher the pump radiation intensity, the higher the effective frequency of the collisions that give rise to a population inversion. Using the carbon monoxide (CO) molecule as an example, we show that when intense (∼1010 W cm⁻²) pump radiation is absorbed in the blue wing of the R branch, a noticeable population inversion can be produced and the gain at the center of the R and P branches of the molecular spectrum can reach 0.011 and 0.250 cm⁻¹ at temperatures T = 300 and 100 K, respectively.     

Energy dependence of vibrational excitation of adsorbed CO and OH

To assess the excitation mechanism of vibrationa modes of adsorbates by electron we have measured loss spectra for CO on Ni (100) and OH on NiO (111) as a function of primary electron energy. We find that the dipole interaction describes the data for the CO system but fails completely for the the OH system. We find the loss intensity in OH to be more than an order of magnitude larger than dipole estimates at low energies. This is accompanied by a strong overtone and intrinsic NiO phonon satellite excitation.     

Threshold peak structures in the vibrational excitation of HCl by low-energy electron impact

A new model which describes dissociative electron attachment and vibrational excitation for the HCl molecule is proposed. The model is based on ab initio scattering data calculated in the fixed nuclei approximation by Morgan et al. [J. Phys. B 23 (1990) 99]. The cross sections for vibrational excitation exhibit interesting oscillatory structures in the threshold peak region.     

High power pure rotational laser due to vibrational excitation

It is suggested for the first time to use VRT-relaxation for the excitation of high power laser laser action on rotational transitions in FIR spectral range. It is shown, that the required conditions can be achieved by the free expansion of the previously heated mixture of hydrogen halides molecules and slowly relaxing molecules.     

Triplet-triplet transfer of electronic energy upon nonequilibrium vibrational excitation of triplet molecules

The specific features of the triplet-triplet (T-T) transfer of electronic excitation energy in a gas phase upon nonequilibrium vibrational excitation of the triplet molecules of a donor were studied for an anthraquinone-diacetyl donor-acceptor pair using the time-resolved slow fluoresence of anthraquinone and sensitized phosphorescence of diacetyl. It is shown that in the gas phase, which allows regular control of the number of collisions, competition between the processes of T-T transfer and intermolecular vibrational relaxation is observed for nanosecond time resolution. The T-T transfer rate for the molecular system investigated exceeded the rate of intermolecular vibrational relaxation k_V in the triplet state T₁ of the donor. The effectiveness of the T-T transfer of energy by vibrationally excited molecules turned out to be higher than the effectiveness of transfer by thermalized ones, but even the highest of them was much less than unity. An increase in the equilibrium temperature of vapors led to a decrease in the effectiveness of transfer for both vibrationally excited and thermalized triplet molecules, thus indicating the importance of the collisional complex in the intermolecular process studied. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 474–479, July–August, 2000.