Parity-resolved state-to-state cross sections for inelastic scattering of NO X (2)Pi(1/2) (upsilon = 20, J = 0.5, elf) from He: A comparison between crossed molecular beams experiments and ab initio theory

被引:38
作者
Drabbels, M
Wodtke, AM
Yang, M
Alexander, MH
机构
[1] UNIV MARYLAND,DEPT CHEM & BIOCHEM,COLLEGE PK,MD 20742
[2] UNIV CALIF SANTA BARBARA,DEPT CHEM,SANTA BARBARA,CA 93106
关键词
D O I
10.1021/jp963898g
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Relative state-to-state cross sections for inelastic collisions between NO X (2) Pi(1/2) (upsilon = 20, J = 0.5, e or f) and He have been determined in a crossed molecular beam setup at a collision energy of 195 cm(-1). Efficient initial state preparation of the NO molecules is achieved by stimulated emission pumping by way of the NO B (2) Pi(1/2) (upsilon = 5) state. The rotational state distribution of the inelastically scattered NO molecules is probed by laser induced fluorescence through the A (2) Sigma(+) (upsilon = 3) state. The measured cross sections are compared with close-coupled quantum scattering calculations on both a recently reported ab initio potential energy surface (PES) and an extension of this PES which takes into account the elongation of the NO bond in upsilon = 20. In the latter calculations, the highly vibrationally excited molecule is treated as a rigid rotor with a bond length equal to the average of the upsilon = 20 level. Even with such an apparently drastic assumption, agreement between the experimental results and the scattering calculations on the latter PES is excellent.
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收藏
页码:6463 / 6474
页数:12
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