Gauge-invariant formulation of time-dependent configuration interaction singles method

TL;DR

This paper develops a gauge-invariant formulation of the TDCIS method for electron dynamics, enabling more stable and efficient simulations in intense laser fields by using velocity gauge with gauge-transformed orbitals.

Contribution

It introduces a gauge-invariant velocity-gauge formulation of TDCIS using gauge-transformed orbitals, improving computational stability and efficiency over traditional length-gauge methods.

Findings

Gauge invariance demonstrated with a 1D helium model

Velocity-gauge formulation avoids divergence issues

Enhanced convergence in intense laser simulations

Abstract

We propose a gauge-invariant formulation of the channel orbital-based time-dependent configuration interaction singles (TDCIS) method [Phys. Rev. A 74, 043420 (2006)], one of the powerful ab initio methods to investigate electron dynamics in atoms and molecules subject to an external laser field. In the present formulation, we derive the equations of motion (EOMs) in the velocity gauge using gauge-transformed orbitals, not fixed orbitals, that are equivalent to the conventional EOMs in the length gauge using fixed orbitals. The new velocity-gauge EOMs avoid the use of the length-gauge dipole operator, which diverges at large distance, and allows to exploit computational advantages of the velocity-gauge treatment over the length-gauge one, e.g, a faster convergence in simulations with intense and long-wavelength lasers, and the feasibility of exterior complex scaling as an absorbing boundary. The reformulated TDCIS method is applied to an exactly solvable model of one-dimensional helium atom in an intense laser field to numerically demonstrate the gauge invariance. We also discuss the consistent method for evaluating the time derivative of an observable, relevant e.g, in simulating high-harmonic generation.