The collisional depolarization of OH(A ²Σ⁺) and NO(A ²Σ⁺) with Kr

Journal article

Quantum beat spectroscopy has been used to measure rate coefficients at 300 K for collisional depolarization for NO(A ²Σ⁺) and OH(A ²Σ⁺) with krypton. Elastic depolarization rate coefficients have also been determined for OH(A) + Kr, and shown to make a much more significant contribution to the total depolarization rate than for NO(A) + Kr. While the experimental data for NO(A) + Kr are in excellent agreement with single surface quasiclassical trajectory (QCT) calculations carried out on the upper 2A ^′ potential energy surface, the equivalent QCT and quantum mechanical calculations cannot account for the experimental results for OH(A) + Kr collisions, particularly at low N. This disagreement is due to the presence of competing electronic quenching at low N, which requires a multi-surface, non-adiabatic treatment. Somewhat improved agreement with experiment is obtained by means of trajectory surface hopping calculations that include non-adiabatic coupling between the ground 1A ^′ and excited 2A ^′ states of OH(X/A) + Kr, although the theoretical depolarization cross sections still significantly overestimate those obtained experimentally.

Authors: Chadwick, H; Brouard, M; Chang, Y; Eyles, C; McCrudden, G

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Institute of Physics Inc.
• Journal: Journal of chemical physics
• Volume: 140
• Issue: 5
• Pages: 054306
• Publication date: 2014-02-04
• DOI: 10.1063/1.4863446
• EISSN: 1089-7690
• ISSN: 0021-9606
• Language: English