Tao Liang, Alexander Millard H
Department of Chemistry and Biochemistry, Institute for Physical Science and Technology, Chemical Physics Program, University of Maryland, College Park, Maryland 20742-2021, USA.
J Chem Phys. 2007 Sep 21;127(11):114301. doi: 10.1063/1.2766716.
Vibrational relaxation of HF(v) in collisions with H atoms can occur by three pathways: inelastic scattering with and without H atom exchange, and, for v>or=3, the HF+H-->F+H2 reaction. Fully quantum, reactive scattering calculations on the Stark-Werner FH2 potential energy surface reveal narrow peaks in the energy dependence of the integral cross sections for each of these processes. By means of an adiabatic-bender analysis, we show that each of these peaks corresponds to the position of quasibound HF-H vibrational states trapped in the weak van der Waals well. The width of these resonances indicates that the lifetime of the quasibound states is up to 30 periods of the HF-H van der Waals vibration.
HF(v) 与H原子碰撞时的振动弛豫可通过三种途径发生:有和没有H原子交换的非弹性散射,以及对于v≥3时的HF + H→F + H₂反应。在Stark-Werner FH₂势能面上进行的全量子反应散射计算揭示了这些过程中每个过程的积分截面能量依赖性中的窄峰。通过绝热弯曲分析,我们表明这些峰中的每一个都对应于被困在弱范德华阱中的准束缚HF-H振动态的位置。这些共振的宽度表明准束缚态的寿命长达HF-H范德华振动的30个周期。