Time-dependent multiconfiguration self-consistent-field method based on occupation restricted multiple active space model for multielectron dynamics in intense laser fields

TL;DR

The paper introduces the TD-ORMAS method, a flexible and efficient approach for simulating multielectron dynamics in intense laser fields by subdividing active orbitals with occupation restrictions, extending previous methods.

Contribution

It develops a new multiconfiguration self-consistent-field method that subdivides active orbitals into multiple groups with occupation restrictions, enabling more flexible and large-active-space simulations.

Findings

Demonstrated effective simulation of multielectron dynamics in lithium hydride models.

Showed cost-effective and systematic approximation capabilities.

Extended the TD-CASSCF framework with greater flexibility.

Abstract

The time-dependent multiconfiguration self-consistent-field method based on the occupation-restricted multiple active space model is proposed (TD-ORMAS) for multielectron dynamics in intense laser fields. Extending the previously proposed time-dependent complete-active-space self-consistent-field method [TD-CASSCF; Phys. Rev. A, {\bf 88}, 023402 (2013)], which divides the occupied orbitals into core and active orbitals, the TD-ORMAS method {\it further} subdivides the active orbitals into an arbitrary number of subgroups, and poses the {\it occupation restriction} by giving the minimum and maximum number of electrons distributed in each subgroup. This enables highly flexible construction of the configuration interaction (CI) space, allowing a large-active-space simulation of dynamics, e.g., the core excitation or ionization. The equations of motion both for CI coefficients and spatial orbitals are derived based on the time-dependent variational principle, and an efficient algorithm is proposed to solve for the orbital time derivatives. In-depth descriptions of the computational implementation are given in a readily programmable manner. The numerical application to the one-dimensional lithium hydride cluster models demonstrates that the high flexibility of the TD-ORMAS framework allows for the cost-effective simulations of multielectron dynamics, by exploiting systematic series of approximations to the TD-CASSCF method.