Hanauer Matthias, Köhn Andreas
Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz, Germany.
J Chem Phys. 2009 Sep 28;131(12):124118. doi: 10.1063/1.3238237.
The recently proposed extension of the explicitly correlated coupled-cluster ansatz using cusp conditions [A. Kohn, J. Chem. Phys. 130, 104104 (2009)] is tested for suitability in the calculation of response properties. For this purpose, static and dynamic electrical properties up to ESHG hyperpolarizabilities as well as optical rotations have been computed within the CCSD(F12) model. It is shown that effectively converged correlation contributions can reliably be obtained using augmented quadruple zeta basis sets already. The ansatz is optionally equipped with an extension capable of reducing the one-electron basis set error. A further simplification of the method specific Lagrangian aimed at reducing the computational effort has been tested and is shown to be uncritical. Furthermore, we examined the impact of conventional triple and quadruple excitations in explicitly correlated property calculations.
针对使用尖点条件的显式相关耦合簇假设[A. 科恩，《化学物理杂志》130, 104104 (2009)]最近提出的扩展，测试了其在响应性质计算中的适用性。为此，在CCSD(F12)模型内计算了直至ESHG超极化率以及旋光性的静态和动态电学性质。结果表明，使用增强四重zeta基组已经能够可靠地获得有效收敛的相关贡献。该假设可选择配备一种能够减少单电子基组误差的扩展。已经测试了旨在减少计算量的方法特定拉格朗日量的进一步简化，结果表明其并无问题。此外，我们研究了传统三重和四重激发在显式相关性质计算中的影响。
