Yang Dongzheng, Liu Lu, Xie Daiqian, Guo Hua
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico, 87131, USA.
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Phys Chem Chem Phys. 2022 Jun 8;24(22):13542-13549. doi: 10.1039/d2cp01230h.
We report the first full-dimensional quantum mechanical calculations of the ro-vibrational inelastic scattering dynamics between water molecules and argon atoms on an accurate potential energy surface, using a recently developed time-independent quantum method based on the close-coupling approach. The state-to-state integral cross-sections and rate coefficients show strong observance of gap laws. The calculated thermal rate coefficients for the relaxation of the stretching fundamental states of HO are in good agreement with experimental values, while those for the bending overtone state are approximately five times smaller than the values extracted through a previous kinetic modeling of fluorescence decay data. Our state-specific quantum scattering results suggest the need to reassess the kinetic modeling of the experimental data. This work advanced our understanding of the quantum dynamics of vibrationally inelastic energy transfer processes involving polyatomic molecules.
我们报道了在精确势能面上水分子与氩原子之间转动 - 振动非弹性散射动力学的首次全维量子力学计算，采用了基于密耦方法最近开发的与时间无关的量子方法。态 - 态积分截面和速率系数表现出对能隙定律的强烈遵循。计算得到的HO伸缩基态弛豫的热速率系数与实验值吻合良好，而弯曲泛音态的热速率系数比通过先前荧光衰减数据的动力学建模提取的值小约五倍。我们的态分辨量子散射结果表明需要重新评估实验数据的动力学建模。这项工作增进了我们对涉及多原子分子的振动非弹性能量转移过程量子动力学的理解。
