期刊
JOURNAL OF CHEMICAL PHYSICS
卷 135, 期 4, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.3615060
关键词
approximation theory; coupled cluster calculations; minimisation; molecular electronic states; variational techniques; wave functions
We show that it is possible to construct an accurate approximation to the variational coupled cluster method, limited to double substitutions, from the minimization of a functional that is rigorously extensive, exact for isolated two-electron subsystems and invariant to transformations of the underlying orbital basis. This approximate variational coupled cluster theory is a modification and enhancement of our earlier linked pair functional theory. It is first motivated by the constraint that the inverse square root of the matrix that transforms the cluster amplitudes must exist. Low-order corrections are then included to enhance the accuracy of the approximation of variational coupled cluster, while ensuring that the computational complexity of the method never exceeds that of the standard traditional coupled cluster method. The effects of single excitations are included by energy minimization with respect to the orbitals defining the reference wavefunction. The resulting quantum chemical method is demonstrated to be a robust approach to the calculation of molecular electronic structure and performs well when static correlation effects are strong. (C) 2011 American Institute of Physics. [doi:10.1063/1.3615060]
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