The correlation discrete variable representation revisited

Abstract

The correlation discrete variable representation (CDVR) enables efficient quantum dynamics calculation with the multi-layer multi-configurational time-dependent Hartree approach on general potential energy surfaces. It employs a time-dependent quadrature to compute potential energy matrix elements, thereby eliminating the need to refit the potential to a sum of products form. The non-hierarchical CDVR conserves the inherent symmetry properties of tree-shaped wavefunction representations and drastically reduces the number of grid points compared to the original hierarchical CDVR. However, it requires projection on the space spanned by the single-hole functions at each node of the tree, which can introduce unphysical couplings for unconverged basis sets. In this work, the non-hierarchical CDVR is revisited, and a revised approach that avoids explicit projection on the single-hole space is introduced. The computational costs of the revised approach scale favorably with the number of single-particle functions (SPFs): for a tree with three edges at each node and n SPFs at each edge, an n4 scaling is achieved. Furthermore, a revised scheme that uses artificial SPFs to systematically increase the accuracy of the CDVR quadrature is presented. Computations studying the photodissociation of NOCl, the vibrational states of methyl, and the non-adiabatic quantum dynamics of photoexcited pyrazine demonstrate the accuracy and efficiency of the revised non-hierarchical CDVR. Notably, for the 24-dimensional pyrazine system, the use of the CDVR does not increase the required wall clock time compared to calculations utilizing the sum of products form of the vibronic coupling model.