波函数
激发态
原子轨道
微扰理论(量子力学)
完整活动空间
量子化学
电子
化学
电子相关
电子结构
量子力学
量子
空格(标点符号)
原子物理学
物理
计算化学
分子
计算机科学
操作系统
超分子化学
出处
期刊:Challenges and advances in computational chemistry and physics
日期:2008-01-01
卷期号:: 125-156
被引量:12
标识
DOI:10.1007/978-1-4020-8184-2_5
摘要
One frequently used quantum chemical approach for studies of spectroscopy and photochemistry is the Complete Active Space (CAS) SCF method in combination with multiconfigurational second order perturbation theory (CASPT2). In this chapter we shall describe these two approaches. The basic idea behind them is the request that the wave function should give a proper description of the electronic structure already at the lowest level of theory. This should be possible for all possible arrangements of the electrons: in chemical bonds, in excited states, in dissociated states, at transition states for chemical reactions, etc. It should also be possible for all atoms of the periodic systems. The CASSCF wave function fulfills, in principle, this requirement because it is full CI, albeit in a limited space of active orbitals. CASSCF can therefore be regarded as an extension of the Hartree-Fock (HF) method to any arrangement of the electrons. The addition of dynamic electron correlation is as crucial here as it is in the HF method. The suggested solution is to compute this energy using second order perturbation theory (CASPT2) because it is relatively simple and allows applications to a wide variety of systems and many electrons. The review will focus on the methods themselves. Applications will be described in other chapters of the book
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