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通讯:二阶多参考微扰理论与显式相关:CASPT2-F12。

Communication: Second-order multireference perturbation theory with explicit correlation: CASPT2-F12.

机构信息

Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.

出版信息

J Chem Phys. 2010 Oct 14;133(14):141103. doi: 10.1063/1.3489000.

Abstract

An explicitly correlated complete active space second-order perturbation (CASPT2-F12) method is presented which strongly accelerates the convergence of CASPT2 energies and properties with respect to the basis set size. A Slater-type geminal function is employed as a correlation factor to represent the electron-electron cusp of the wave function. The explicitly correlated terms in the wave function are internally contracted. The required density matrix elements and coupling coefficients are the same as in conventional CASPT2, and the additional computational effort for the F12 correction is small. The CASPT2-F12 method is applied to the singlet-triplet splitting of methylene, the dissociation energy of ozone, and low-lying excited states of pyrrole.

摘要

本文提出了一种完全活性空间二阶微扰(CASPT2-F12)方法,该方法可以大大加速 CASPT2 能量和性质对基组大小的收敛。采用 Slater 型双子函数作为相关因子来表示波函数的电子电子余割。波函数中的显式相关项在内部进行收缩。所需的密度矩阵元素和耦合系数与传统 CASPT2 相同,F12 校正的额外计算工作量很小。CASPT2-F12 方法应用于亚甲基的单重态-三重态分裂、臭氧的离解能以及吡咯的低能激发态。

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