Time-Dependent Complete-Active-Space Self-Consistent-Field Method for Ultrafast Intense Laser Science

TL;DR

The paper introduces a novel time-dependent complete-active-space self-consistent-field (TD-CASSCF) method for simulating multielectron dynamics in atoms and molecules under ultrafast intense laser fields, enabling accurate first-principles analysis.

Contribution

It develops a flexible, gauge-invariant, and size-extensive TD-CASSCF approach with efficient boundary conditions for realistic ultrafast laser simulations.

Findings

Successfully simulated ionization yields, high-harmonic spectra, and photoelectron spectra.

Demonstrated the method's accuracy and efficiency in full-dimensional atomic calculations.

Provided a foundation for ab initio studies of ultrafast laser interactions with complex systems.

Abstract

We present the time-dependent complete-active-space self-consistent-field (TD-CASSCF) method to simulate multielectron dynamics in ultrafast intense laser fields from the first principles. While based on multiconfiguration expansion, it divides the orbital space into frozen-core (tightly bound electrons with no response to the field), dynamical-core (electrons tightly bound but responding to the field), and active (fully correlated to describe highly excited and ejected electrons) orbital subspaces. The subspace decomposition can be done flexibly, conforming to phenomena under investigation and desired accuracy. The method is gauge invariant and size extensive. Infinite-range exterior complex scaling in addition to mask-function boundary is adopted as an efficient absorbing boundary. We show numerical examples and illustrate how to extract relevant physical quantities such as ionization yield, high-harmonic spectrum, and photoelectron spectrum from our full-dimensional implementation for atoms. The TD-CASSCF method will open a way to the ab initio simulation study of ultrafast intense laser science in realistic atoms and molecules.