Layered discrete variable representations and their application within the multiconfigurational time-dependent Hartree approach

Abstract

The multiconfigurational time-dependent Hartree (MCTDH) approach facilitates multidimensional quantum dynamics calculations by employing a layered representation: in the upper layer of the representation the multidimensional wave function is expanded in a basis of time-dependent single-particle functions, in the lower layer then these single-particle functions are represented in a larger time-independent basis. This two layer approach can be generalized to a multilayer MCTDH representation to further increase the numerical efficiency. In recent work [U. Manthe, J. Chem. Phys. 128, 164116 (2008)], a quadrature scheme has been introduced which facilitates multilayer MCTDH calculations for Hamiltonians with general potential energy functions. Based on time-dependent discrete variable representation (DVR) grids corresponding to the single-particle function bases the scheme employs the correlation DVR (CDVR) approach. The present work shows that serious problems arise when this original multilayer CDVR approach is applied for accurate calculations of vibrational states. A solution to these problems is presented which uses a revised scheme to define the time-dependent DVR grids entering into the CDVR scheme. Applications studying the vibrational states of CH(3) demonstrate that the resulting revised multilayer MCTDH/CDVR approach yields smoothly convergent and accurate results.