Abstract

The cross sections and rate constants of pure rotational and ro-vibrational inelastic collision processes for the D₂–HF system were investigated by employing the recently developed coupled-states approximation including the nearest neighbor Coriolis couplings, based on our newly constructed potential energy surface. The state-to-state cross sections and rate constants were found to follow the usual energy and angular momentum gap laws for pure rotational and ro-vibrational energy transfer processes. The calculated rate constant of 1.18 × 10^-10 cm³ mol⁻¹ s⁻¹ for D₂(v₁=0) + HF(v₂=0, j₂=13) is very close to the experimental value of (1.2 ± 0.2) × 10^-10 cm³ mol⁻¹ s⁻¹. The calculated vibrational-resolved rate constants are in reasonably consistent to the available experimental results and follow the similar trend with temperature.

Graphical abstract

中文翻译：

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HF与D 2碰撞的能量转移量子动力学的理论研究。

摘要

基于最近构造的势能面，采用最近开发的耦合状态近似方法，包括最近邻科里奥利耦合，研究了D ₂ -HF系统纯旋转和振动振动非弹性碰撞过程的横截面和速率常数。发现状态间的横截面和速率常数遵循纯能量和角动量间隙定律，适用于纯旋转和旋转振动能量传递过程。对于D ₂（v ₁ = 0）+ HF（v ₂ = 0，j ₂），计算出的速率常数为1.18×10 ^-10 cm ³ mol ^-1 s ^-1= 13）非常接近（1.2±0.2）×10 ^-10 cm ³ mol ^-1 s ^-1的实验值。计算得到的振动分辨速率常数与可用的实验结果基本一致，并且随温度变化遵循相似的趋势。

图形概要