Explicitly correlated second-order perturbation theory calculations on molecules containing heavy main-group elements

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• 作者：Florian A. Bischoff ; Sebastian H?fener ; Andreas Gl?? and Wim Klopper
• 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
• 出版年：2008
• 出版时间：September, 2008
• 年：2008
• 卷：121
• 期：1-2
• 页码：11-19
• 全文大小：727.3 KB

文摘

Slater-type geminals (STGs) have been used as explicitly correlated two-electron basis functions for calculations on the hydrides of N–As and Sb (as well as on the hydrides of O–Se and F–Br with similar, not reported results) in various one-electron basis sets of Gaussian atomic orbitals. The performance of the explicitly correlated theory has been assessed with respect to the exponent of the STG, for example, by using different exponents for individual pair correlation functions and pair energies. It is shown that a correlation factor with an exponent of g = 1.4 a₀-1{\gamma = 1.4 a_{0}^{-1}} can give reliable results within 1 % from the basis-set limit for all investigated molecules in an aug-cc-pVQZ basis set for the valence shells, using fixed amplitudes for the STGs in a diagonal orbital-invariant formulation of the theory. The use of relativistic effective core potentials (RECPs) in explicitly correlated second-order perturbation theory has been investigated.