title: Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. IV. The automatic implementation of the Hessian based VBSCF method.
abstract: In this paper, the Hessian matrix of valence bond (VB) self-consistent field (VBSCF) energy with respect to orbitals are evaluated by applying the nonorthogonal orbital based N-body reduced density matrices, which was presented in Paper I. To this end, an automatic formula/code generator (AFCG) is developed; with which the matrix elements between internally contracted excited configurations of VB wave function and the corresponding codes are generated automatically. Compared to the tedious manual formula deducing and implementing, AFCG is much more convenient and efficient, and enables us to avoid troublesome debugging. With the help of AFCG, the Hessian-based Newton-Raphson algorithm is implemented for the VBSCF orbital optimization. Test calculations indicate that the Newton-Raphson algorithm converges quadratically and has much better convergence behavior than the gradient-based LBFGS algorithms. Furthermore, a combined approach with LBFGS and Newton-Raphson algorithms is applied to reduce the total CPU time of the calculation.
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
authors.forename: Xun
authors.initials: X
authors.lastname: Chen
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
authors.forename: Zhenhua
authors.initials: Z
authors.lastname: Chen
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Wu