Vibrational Energy Transfer between CO and COS: A Test of the Harmonic Oscillator Model

The contribution of long-range forces to the observed rates of V 4 V energy transfer processes has been studied. The theoretical model uses the first order perturbation approximation to generate a probability function, with the dipoledipole perturbing potential as given by Margenau: Vir = [( 1/6)1/2pl.p2]R-3. The probability function derived is shown to be a strong function of the energy mismatch between the IR bands of the colliding molecules. The calculation emphasizes the importance of rotational state population effects, the most important J states being those which minimize tbe energy mismatch. A complete analysis of energy transfer between CO(u) and COS(OO0) where v = 1,2, . . . 13 is presented. The calculation reveals the importance of combination bands in the energy transfer mechanism of polyatomics. The temperature dependence for near-resonant processes is also studied and the importance of the V + R energy transfer leads to the classification of 00 (band-center energy mismatch) into three categories small, medium, and large, according to the temperature dependence that the corresponding processes exhibit. The predictions of the theoretical model are compared to experimental data for the same system.

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Vibrational energy transfer in near resonance due to dipole–dipole interactions

Lev‐on

Palke

Millikan

1973

Int J of Chemical Kinetics

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Vibrational relaxation of carbon monoxide by foreign gases

Kovacs¹

1973

The Journal of Chemical Physics

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Measurement of the rate of excitation and deactivation of OCS(001), N2O(001), CS2(001), and C2N2(00100) using laser excited CO as a pumping source

Hancock

Starr

Green

1974

The Journal of Chemical Physics

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The laser fluorescence method has been used to measure CO( v = I) collisional transfer rates in several binary and ternary gas mixtures at 296 oK. Excitation of the CO(v = 1) level was achieved using pulsed 4.6 porn radiation from a frequency doubled CO, laser. The relative inertness of CO molecules towards V ~ T deactivation greatly facilitates the study of vibrational relaxation rates of the additive species in selected cases. In this paper, intermolecular V ~ V transfer rates at 296°K are reported for CO(v = I) with N,O, OCS, SO" CS,' C,N" and for CO(v =2) with CO. In addition, the additive deactivation rates were determined for the following collisional processes: N ,0(00 I) with N,O, CO, Ar; OCS(OOI) with OCS, CO, Ar; CS,(OOI) with CS" CO; and C,N,(OOIOO) with C,N, and CO.Precautions taken to assure high gas purity have been reported previously. I All condensable gases were freeze-pumped and outgassed at 77 OK. The gases CzN z , CS z , and OCS were further purified by trap-to-trap distillation. The middle fractions were withdrawn for sample use. Carbon monoxide and Ar were stored under liquid N z several hours prior to sample preparation.

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Vibrational Energy Transfer between CO and COS: A Test of the Harmonic Oscillator Model

Cited by 5 publications

References 6 publications

Vibrational energy transfer in near resonance due to dipole–dipole interactions

Vibrational energy transfer in near resonance due to dipole–dipole interactions

Vibrational relaxation of carbon monoxide by foreign gases

Measurement of the rate of excitation and deactivation of OCS(001), N2O(001), CS2(001), and C2N2(00100) using laser excited CO as a pumping source

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