Quantum mechanics of local mode ABA triatomic molecules
Quantum mechanics of local mode ABA triatomic molecules
复制标题
局域模式ABA三原子分子的量子力学
DOI：
10.1063/1.444261
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发表时间：
1982
影响因子：
4.4
通讯作者：
W. Reinhardt
中科院分区：
文献类型：
--
作者：
E. Sibert;J. Hynes;W. Reinhardt
研究了三原子分子局域模振动伸缩动力学的量子力学。以H2O模型为原型。量子分析利用了相应的经典分析的同伴文件，其中一个近似的，但准确的哈密顿量是通过非线性力学的技术。量子化这个哈密顿给出了H2O的振动能量与直接量子计算非常一致。H2O模型的相应泛音组合谱在局部和简正模式行为方面借助于由哈密顿量提供的双重受阻转子视角进行分析。光谱中的分裂与能量转移的量子动力学有关。一个半经典的WKB分析也被用来与经典的能量转移率和量子动力学隧道和反射概率的分裂。
The quantum mechanics of the vibrational stretching dynamics in ’’local mode’’ triatomic molecules is examined. A model for H2O is taken as a prototype. The quantum analysis exploits the corresponding classical analysis of the companion paper, in which an approximate but accurate Hamiltonian is derived via the techniques of nonlinear mechanics. Quantization of this Hamiltonian gives H2O vibrational energies in excellent agreement with direct quantum calculations. The corresponding overtone‐combination spectrum of the H2O model is analyzed in terms of local and normal mode behavior with the aid of the twofold hindered rotor perspective provided by the Hamiltonian. The splittings in the spectrum are related to the quantum dynamics of energy transfer. A semiclassical WKB analysis is also used to relate the splittings to classical energy transfer rates and quantum dynamical tunneling and reflection probabilities.