期刊
JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 30, 期 3, 页码 399-406出版社
WILEY
DOI: 10.1002/jcc.21065
关键词
gradient; valence bond theory; nonorthogonal orbitals; ab initio
资金
- Natural Science Foundation of China [20533010, 20403013]
- National Basic Research Program of China [2004CB719902]
An efficient algorithm for energy gradients in valence bond theory with nonorthogonal orbitals is presented. A general Hartree-Fock-like expression for the Hamiltonian matrix element between valence bond (VB) determinants is derived by introducing a transition density matrix. Analytical expressions for the energy gradients with respect to the orbital coefficients are obtained explicitly, whose scaling for computational cost is m(4) where m is the number of basis functions. and is thus approximately the same as in HF method. Compared with other existing approaches. the present algorithm has lower scaling, and thus is much more efficient. Furthermore, the expression for the energy gradient with respect to the nuclear coordinates is also presented, and it provides an effective algorithm for the geometry optimization and the evaluation of various molecular properties in VB theory. Test applications show that our new algorithm runs faster than other methods. (C) 2008 Wiley Periodicals, Inc.
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