Lundbeck Foundation Center for Theoretical Chemistry, Center for Oxygen Miscroscopy and Imaging, Department of Chemistry, Aarhus University, DK-8000 Århus C, Denmark.
Phys Chem Chem Phys. 2012 May 21;14(19):6672-87. doi: 10.1039/c2cp40090a. Epub 2012 Apr 10.
This perspective addresses selected recent developments in the theoretical calculation of vibrational spectra, energies, wave functions and properties. The theoretical foundation and recently developed computational protocols for constructing hierarchies of vibrational Hamiltonian operators are reviewed. A many-mode second quantization (SQ) formulation is discussed prior to the discussion of anharmonic wave functions. Emphasis is put on vibrational self-consistent field (VSCF) based methods and in particular vibrational coupled cluster (VCC) theory. Other issues are also reviewed briefly, such as inclusion of thermal effects, response theoretical calculation of spectra, and the difficulty in treating dense spectra.
本文着眼于理论计算振动光谱、能量、波函数和性质方面的一些最新进展。综述了构建振动哈密顿算子层次结构的理论基础和最新开发的计算方案。在讨论非谐波函数之前，先讨论了多模二次量子化（SQ）表述。重点介绍了基于振动自洽场（VSCF）的方法，特别是振动耦合簇（VCC）理论。还简要回顾了其他一些问题，如热效应的包含、光谱的响应理论计算以及处理密集光谱的困难。
