Publication Abstracts
Green et al. 1986
, D.L. Cochrane, and D.G. Truhlar, 1986: Accuracy of the energy-conrrected sudden (ECS) scaling procedure for rotational excitation of CO by collisions with Ar. J. Chem. Phys., 84, 3865-3869, doi:10.1063/1.450097.
We examine the question, given a set of state-to-state rate constants k(j=0→j'|T) for collision-induced rotational transitions in a diatomic molecule, where j and j' are initial and final rotational quantum numbers and T is the tranlational temperature, can one use scaling analyses to predict a full set of j→j' rate constants? To answer this we consider a rigid rotator model of CO in a bath of Ar at 500 K, and we calculate accurate quasiclassical k(j=0→j'|T) for j=0, 10, and 20 and j'=0-29. These are used to test the energy sudden (ES) and energy-corrected sudden (ECS) scaling procedures. Both procedures are used to predict the j=10 and j=20 rate constants from the j=0 values. The ES procedure, which has no adjustable parameters, overestimates the rates out of excited states by a factor of about 1.5 with a rms error of about 60%. The ECS procedure, in contrast, when the one parameter bc (a critical impact parameter) is about 1.75-2.0 Å, yields excellent excited-state rates on the average and has a rms error of less than 20%. The value of bc can be estimated by a weighted average impact parameter leading to inelastic collisions from a j=0 inital state.
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BibTeX Citation
@article{gr09100s, author={Green, S. and Cochrane, D. L. and Truhlar, D. G.}, title={Accuracy of the energy-conrrected sudden (ECS) scaling procedure for rotational excitation of CO by collisions with Ar}, year={1986}, journal={Journal of Chemical Physics}, volume={84}, pages={3865--3869}, doi={10.1063/1.450097}, }
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RIS Citation
TY - JOUR ID - gr09100s AU - Green, S. AU - Cochrane, D. L. AU - Truhlar, D. G. PY - 1986 TI - Accuracy of the energy-conrrected sudden (ECS) scaling procedure for rotational excitation of CO by collisions with Ar JA - J. Chem. Phys. JO - Journal of Chemical Physics VL - 84 SP - 3865 EP - 3869 DO - 10.1063/1.450097 ER -
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