A non-hierarchical multi-layer multi-configurational time-dependent Hartree approach for quantum dynamics on general potential energy surfaces.

ABSTRACT

The correlation discrete variable representation (CDVR) enables multi-layer multi-configurational time-dependent Hartree (MCTDH) quantum dynamics simulations on general potential energy surfaces. In a recent study [R. Ellerbrock and U. Manthe, J. Chem. Phys. 156, 134107 (2022)], an improved CDVR that can account for the symmetry properties of a tree-shaped wavefunction representation has been introduced. This non-hierarchical CDVR drastically reduces the number of grid points required in the time-dependent quadrature used to evaluate all potential energy matrix elements. While the first studies on the non-hierarchical CDVR approach have been restricted to single-layer calculations, here the complete theory required for the implementation of the non-hierarchical CDVR approach in the multi-layer MCTDH context will be presented. Detailed equations facilitating the efficient recursive computation of all matrix elements are derived, and a new notation adapted to the symmetry properties of the tree-shaped representation is introduced. Calculations studying the non-adiabatic quantum dynamics of photoexcited pyrazine in 24 dimensions illustrate the properties of the non-hierarchical multi-layer CDVR.