The collisional depolarization of (2S+1)Sigma radicals by closed shell atoms: Theory and application to OH(A (2)Sigma(+))+Ar.

Journal article

Classical and quantum mechanical expressions for the j-j(') vector correlation (also referred to as the rotational tilt) are presented for the situation in which the initial and final relative velocity directions are unresolved. The quantum mechanical expressions are compared with previous descriptions in the literature. It is shown that in the case of (2S+1)Sigma radicals in collision with closed shell species, a tensor opacity formalism can be employed in quasiclassical trajectory calculations to provide classical estimates of both open shell spin-rotation state and nuclear hyperfine state changing (or conserving) cross sections. Polarization parameters are also obtained from the same formalism. The method is applied to calculations on the OH(A (2)Sigma(+))-Ar system using a recently developed potential energy surface. The results of both the closed and open shell quasiclassical trajectory calculations are found to compare favorably with those from close-coupled closed and open shell quantum mechanical scattering calculations. The accompanying paper provides an experimental test of these calculations and of the potential energy surface they employ.

Authors: Aoiz, F; Brouard, M; Eyles, C; Kłos, J; Miranda, d

• Publication status: Published
• Journal: Journal of chemical physics
• Volume: 130
• Issue: 4
• Pages: 044305
• Publication date: 2009-01-01
• DOI: 10.1063/1.3061496
• EISSN: 1089-7690
• ISSN: 0021-9606
• Language: English
• Keywords: potential energy surfaces; spin-rotation coupling; atom-molecule collisions; hyperfine structure; oxygen compounds; argon; free radicals