On the gauge invariance of nonperturbative electronic dynamics using the time-dependent Hartree-Fock and time-dependent Kohn-Sham

Citation:

Ding, F., Liang, W., Chapman, C. T., Isborn, C. M., & Li, X. (2011). On the gauge invariance of nonperturbative electronic dynamics using the time-dependent Hartree-Fock and time-dependent Kohn-Sham. Journal of Chemical Physics, 135, 164101.

Abstract:

Nonperturbative electronic dynamics using the time-dependent Hartree-Fock (TDHF) and time-dependent Kohn-Sham (TDKS) theories with the adiabatic approximation is a powerful tool in obtaining insights into the interaction between a many-electron system and an external electromagnetic field. In practical applications of TDHF/TDKS using a truncated basis set, the electronic dynamics and molecular properties become gauge-dependent. Numerical simulations are carried out in the length gauge and velocity gauge to verify the extent of gauge-dependence using incomplete basis sets. Electronic dynamics of two many-electron systems, a helium atom and a carbon monoxide molecule in high-intensity linearly polarized radiation fields are performed using the TDHF and TDKS with two selected adiabatic exchange-correlation (xc) functionals. The time evolution of the expectation values of the dipole moment and harmonic spectra are calculated in the two gauges, and the basis set dependence on the gauge-invariance of these properties is investigated.