Generalized vibrational perturbation theory for rotovibrational energies of linear, symmetric and asymmetric tops: Theory, approximations, and automated approaches to deal with medium-to-large molecular systems

被引:100
作者
Piccardo, Matteo [1 ]
Bloino, Julien [1 ,2 ]
Barone, Vincenzo [1 ]
机构
[1] Scuola Normale Super Pisa, I-56126 Pisa, Italy
[2] CNR, Ist Chim Composti Organometall CNR ICCOM UOS Pisa, I-56124 Pisa, Italy
基金
欧洲研究理事会;
关键词
VPT2; anharmonicity; symmetric molecules; generalized vibrational perturbation theory; anharmonic resonances; SELF-CONSISTENT-FIELD; QUARTIC FORCE-FIELD; CENTRIFUGAL-DISTORTION COEFFICIENTS; RESOLUTION INFRARED-SPECTRUM; AB-INITIO CALCULATION; GAUSSIAN-TYPE BASIS; DANS LES MOLECULES; POLYATOMIC-MOLECULES; PARTITION-FUNCTIONS; EQUILIBRIUM STRUCTURE;
D O I
10.1002/qua.24931
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Models going beyond the rigid-rotor and the harmonic oscillator levels are mandatory for providing accurate theoretical predictions for several spectroscopic properties. Different strategies have been devised for this purpose. Among them, the treatment by perturbation theory of the molecular Hamiltonian after its expansion in power series of products of vibrational and rotational operators, also referred to as vibrational perturbation theory (VPT), is particularly appealing for its computational efficiency to treat medium-to-large systems. Moreover, generalized (GVPT) strategies combining the use of perturbative and variational formalisms can be adopted to further improve the accuracy of the results, with the first approach used for weakly coupled terms, and the second one to handle tightly coupled ones. In this context, the GVPT formulation for asymmetric, symmetric, and linear tops is revisited and fully generalized to both minima and first-order saddle points of the molecular potential energy surface. The computational strategies and approximations that can be adopted in dealing with GVPT computations are pointed out, with a particular attention devoted to the treatment of symmetry and degeneracies. A number of tests and applications are discussed, to show the possibilities of the developments, as regards both the variety of treatable systems and eligible methods. (c) 2015 Wiley Periodicals, Inc.
引用
收藏
页码:948 / 982
页数:35
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