Yang Benhui, Stancil P C, Balakrishnan N, Forrey R C
Department of Physics and Astronomy, The University of Georgia, Athens, Georgia 30602-2451, USA.
J Chem Phys. 2006 Mar 14;124(10):104304. doi: 10.1063/1.2178299.
Quantum close-coupling and coupled-states approximation scattering calculations of rotational energy transfer in CO due to collisions with H2 are presented for collision energies between 10(-6) and 15,000 cm(-1) using the H2-CO interaction potentials of Jankowski and Szalewicz [J. Chem. Phys. 123, 104301 (2005); 108, 3554 (1998)]. State-to-state cross sections and rate coefficients are reported for the quenching of CO initially in rotational levels j2 = 1-3 by collisions with both para- and ortho-H2. Comparison with the available theoretical and experimental results shows good agreement, but some discrepancies with previous calculations using the earlier potential remain. Interestingly, elastic and inelastic cross sections for the quenching of CO (j2 = 1) by para-H2 reveal significant differences at low collision energies. The differences in the well depths of the van der Waals interactions of the two potential surfaces lead to different resonance structures in the cross sections. In particular, the presence of a near-zero-energy resonance for the earlier potential which has a deeper van der Waals well yields elastic and inelastic cross sections that are about a factor of 5 larger than that for the newer potential at collision energies lower than 10(-3) cm(-1).
利用扬科夫斯基和萨莱维茨的H₂ - CO相互作用势[《化学物理杂志》123, 104301 (2005); 108, 3554 (1998)],给出了在10⁻⁶至15000 cm⁻¹碰撞能量范围内,H₂与CO碰撞时转动能量转移的量子密耦和耦合态近似散射计算结果。报告了CO初始处于转动能级j₂ = 1 - 3时,与仲氢和正氢碰撞猝灭的态 - 态截面和速率系数。与现有的理论和实验结果比较显示出良好的一致性,但与使用早期势的先前计算仍存在一些差异。有趣的是,仲氢猝灭CO (j₂ = 1)的弹性和非弹性截面在低碰撞能量下显示出显著差异。两个势面范德华相互作用阱深的差异导致截面中出现不同的共振结构。特别是,对于具有更深范德华阱的早期势,在碰撞能量低于10⁻³ cm⁻¹时,存在一个近零能量共振,其弹性和非弹性截面比新势的大约大5倍。