Self‐relaxation of vibrationally excited H2O molecules
Self‐relaxation of vibrationally excited H2O molecules
复制标题
振动激发的 H2O 分子的自弛豫
DOI：
10.1063/1.464230
复制
发表时间：
1993
影响因子：
4.4
通讯作者：
H. Shin
中科院分区：
文献类型：
--
作者：
H. Shin
这项关于振动激发的H2O分子的自弛豫的研究是基于一个模型，在这个模型中，一个激发的分子和它的碰撞伙伴在强分子吸引力的存在下经历了一个长寿命的碰撞。跃迁几率是通过使用阶梯算子的半经典过程得到的。研究表明，大碰撞参数碰撞是导致H2O（001）→H2O（020）、H2O（020）→ H2O（010）和H2O（010）→H2O（000）VV跃迁几率负温度依赖性的原因。这些能量转移过程发生在分子内，并且发现由VV过程释放的振动能量失配转移到复合物中的低频氧-氧运动是非常有效的，而能量转移到受激分子的受阻旋转运动是低效的。该模型预测VV概率减少氘。
This study on the self‐relaxation of vibrationally excited H2O molecules is based on a model in which an excited molecule and its collision partner undergo a long‐lived collision in the presence of strong molecular attraction. Transition probabilities are obtained by semiclassical procedures using ladder operators. The study shows that large‐impact parameter collisions are responsible for the negative temperature dependence of the VV transition probabilities in H2O(001)→H2O(020), H2O(020)→H2O(010), and H2O(010)→H2O(000). These energy transfer processes occur intramolecularly, and the transfer of the vibrational energy mismatch that is released by the VV process to the low frequency oxygen–oxygen motion in the complex is found to be very efficient, whereas energy transfer to the hindered rotational motions of the excited molecule is inefficient. The model predicts VV probabilities to decrease on deuteration.