Modelling non-adiabatic effects in H₃⁺: solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces.
Modelling non-adiabatic effects in H₃⁺: solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces.
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模拟 H₃⁺ 中的非绝热效应：具有运动相关质量和质量表面的旋转薛定谔方程的解。
DOI：
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发表时间：
2014
影响因子：
4.4
通讯作者：
A. Császár
中科院分区：
文献类型：
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作者：
E. Mátyus;Tamás Szidarovszky;A. Császár
在核运动哈密顿量中引入不同的旋转和振动质量是模拟旋转振动非绝热性的一种简单的现象学方法。以分子离子H3（+）为例表明，存在精确到小于0.1 cm（-1）的全局绝热势能面[M]。Pavanello， L. Adamowicz， A. Alijah， N. F. Zobov， I. I. Mizus， O. L. Polyansky， J. Tennyson， T. Szidarovszky， A. G. Császár， M. Berg等，物理学。Rev. Lett. 108, 023002(2012)]，运动依赖的质量概念产生了更准确的旋转振动能级，但不同寻常的是，结果取决于分子固定框架嵌入的选择。采用D（3h）点群对称参考结构对应的Eckart嵌入，得到了正确的简并并与实验数据更加吻合。H3（+）中质子的振动质量通过最小化计算值与最近高精度实验跃迁之间的均方根（rms）偏差来优化。得到的最佳振动质量比质子的核质量大大约三分之一电子质量，m(opt,p)((v))=m(nuc,p)+0.31224m(e)。这种优化的振动质量，加上核旋转质量，将实验和计算的旋转振动跃迁的均方根偏差降低了一个数量级。最后，证明了该算法的扩展允许使用运动相关质量，也可以处理旋转振动哈密顿量中与坐标相关的质量曲面。
Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H3(+), for which a global adiabatic potential energy surface accurate to better than 0.1 cm(-1) exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon the choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D(3h) point-group symmetry is employed. The vibrational mass of the proton in H3(+) is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m(opt,p)((v))=m(nuc,p)+0.31224m(e). This optimized vibrational mass, along with a nuclear rotational mass, reduces the rms deviation of the experimental and computed rovibrational transitions by an order of magnitude. Finally, it is shown that an extension of the algorithm allowing the use of motion-dependent masses can deal with coordinate-dependent mass surfaces in the rovibrational Hamiltonian, as well.
使用非直积基础计算 H3( ) 的 J > 0 旋转状态
DOI：
10.1021/jp312027s
发表时间：
2013
期刊：
The journal of physical chemistry. A
影响因子：
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作者：
R. Jaquet;T. Carrington
通讯作者：
T. Carrington