Jump to main content
Jump to site search

Issue 23, 2002
Previous Article Next Article

Rotational energy transfer in collisions of CH A2Δ, v = 0 with Ar, N2 and CO2

Author affiliations

Abstract

Rotational energy transfer (RET) in collisions of CH A2Δ, v = 0 with Ar, N2 and CO2 has been investigated experimentally. Laser excitation was used to prepare selected initial levels N = 2,3,5 (all colliders), 8 (Ar and CO2) and 14 (Ar only). Additional fine-structure state selection was achieved for the lower levels, and Λ-doublet selection for the higher levels. Total and state-to-state RET rate constants were extracted from time-resolved dispersed fluorescence spectra. Partial fine-structure-state resolution was possible for N′ ⩽ 4, and Λ-doublet resolution for the highest levels. For Ar, good absolute agreement was found with previous state-selective experimental work and ab initio theoretical predictions. RET is substantially more efficient for N2 and CO2, for which the first reliable absolute rate constants are provided. A change of fine-structure state with ΔN = 0 is the most probable single state-to-state channel at low N for all three partners. Partial conservation of the fine-structure label during ΔN ≠ 0 collisions, previously observed for Ar, was found to extend to the other partners. The relative ΔN propensities are similar for all three partners. This is consistent with a simple impulsive model of the collision dynamics, in which energy constraints dominate because of the large rotational energy spacing characteristic of hydrides. This model does not, however, provide a straightforward explanation for the substantial differences in RET efficiency for Ar, N2 and CO2.

Back to tab navigation

Publication details

The article was received on 02 Aug 2002, accepted on 01 Oct 2002 and first published on 23 Oct 2002


Article type: Paper
DOI: 10.1039/B207590N
Citation: Phys. Chem. Chem. Phys., 2002,4, 5768-5777
  •   Request permissions

    Rotational energy transfer in collisions of CH A2Δ, v = 0 with Ar, N2 and CO2

    H. J. Crichton, C. Murray and K. G. McKendrick, Phys. Chem. Chem. Phys., 2002, 4, 5768
    DOI: 10.1039/B207590N

Search articles by author

Spotlight

Advertisements