TY - JOUR

T1 - Accuracy of the energy-corrected sudden (ECS) scaling procedure for rotational excitation of CO by collisions with Ar

AU - Green, Sheldon

AU - Cochrane, David L.

AU - Truhlar, Donald G.

PY - 1985

Y1 - 1985

N2 - 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 translational 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→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 7=0 initial state.

AB - 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 translational 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→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 7=0 initial state.

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U2 - 10.1063/1.450097

DO - 10.1063/1.450097

M3 - Article

AN - SCOPUS:36549095336

SN - 0021-9606

VL - 84

SP - 3865

EP - 3869

JO - The Journal of chemical physics

JF - The Journal of chemical physics

IS - 7

ER -