Effects of electronic correlation on the high harmonic generation in helium: A time-dependent configuration interaction singles vs time-dependent full configuration interaction study

Abstract

In this paper, we investigate the effects of full electronic correlation on high harmonic generation in the helium atom subjected to laser pulses of extremely high intensity. To do this, we perform real-time propagations of helium atom wavefunction using quantum chemistry methods coupled to Gaussian basis sets. Calculations are performed within the real-time time-dependent configuration interaction framework at two levels of theory: time-dependent configuration interaction with single excitations (uncorrelated method) and time-dependent full configuration interaction (fully correlated method). The electronic wavefunction is expanded in Dunning basis sets supplemented with functions adapted to describing highly excited and continuum states. We also compare the time-dependent configuration interaction results with grid-based propagations of the helium atom within the single-active-electron approximation. Our results show that when including the dynamical electron correlation, a noticeable improvement to the description of high harmonic generation (HHG) can be achieved in terms of, e.g., a more constant intensity in the lower energy part of the harmonic plateau. However, such effects can be captured only if the basis set used suffices to reproduce the most basic features, such as the HHG cutoff position, at the uncorrelated level of theory.