Spectroscopy of H3+ based on a new high-accuracy global potential energy surface
Spectroscopy of H3+ based on a new high-accuracy global potential energy surface
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基于新型高精度全局势能面的H3光谱分析
DOI：
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
A. Császár
中科院分区：
文献类型：
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作者：
O. Polyansky;A. Alijah;N. Zobov;I. Mizus;R. Ovsyannikov;J. Tennyson;L. Lodi;Tamás Szidarovszky;A. Császár
分子离子是最简单的多原子和多电子分子系统，其光谱构成了一个重要的基准，可以从量子力学方程从头开始获得精确的答案。本文讨论了在振转光谱计算方面的重要进展。最近，一个新的、基于从头算点的全球势能面（PES）被构建出来，相对于非相对论极限的平均精度为0.01 cm−1。提供了这些点的分析表示，标准偏差为0.097 cm−1。与早期配合的问题进行了讨论。新的PES用于计算过渡频率。最近在可见光波长下测量的谱线与先前确定的红外振转数据相结合，表明这些计算可以达到0.1 cm−1的精度。为了达到这种程度的准确性，相对论，绝热和非绝热效应必须适当占。这些计算的准确性有助于重新分配一些测量线，进一步减少实验和理论之间的标准偏差。
The molecular ion is the simplest polyatomic and poly-electronic molecular system, and its spectrum constitutes an important benchmark for which precise answers can be obtained ab initio from the equations of quantum mechanics. Significant progress in the computation of the ro–vibrational spectrum of is discussed. A new, global potential energy surface (PES) based on ab initio points computed with an average accuracy of 0.01 cm−1 relative to the non-relativistic limit has recently been constructed. An analytical representation of these points is provided, exhibiting a standard deviation of 0.097 cm−1. Problems with earlier fits are discussed. The new PES is used for the computation of transition frequencies. Recently measured lines at visible wavelengths combined with previously determined infrared ro–vibrational data show that an accuracy of the order of 0.1 cm−1 is achieved by these computations. In order to achieve this degree of accuracy, relativistic, adiabatic and non-adiabatic effects must be properly accounted for. The accuracy of these calculations facilitates the reassignment of some measured lines, further reducing the standard deviation between experiment and theory.