On the Proper Derivation of the Floquet-based Quantum Classical Liouville Equation and Surface Hopping Describing a Molecule or Material Subject to an External Field

Abstract

We investigate two approaches to derive the proper Floquet-based quantum-classical Liouville equation (F-QCLE) for laser-driven electron-nuclear dynamics. The first approach projects the operator form of the standard QCLE onto the diabatic Floquet basis, then transforms to the adiabatic representation. The second approach directly projects the QCLE onto the Floquet adiabatic basis. Both approaches yield a form which is similar to the usual QCLE with two modifications: 1. The electronic degrees of freedom are expanded to infinite dimension. 2. The nuclear motion follows Floquet quasi-energy surfaces. However, the second approach includes an additional cross derivative force due to the dual dependence on time and nuclear motion of the Floquet adiabatic states. Our analysis and numerical tests indicate that this cross derivative force is a factitious artifact, suggesting that one cannot safely exchange the order of Floquet state projection with adiabatic transformation. Our results are in accord with similar findings by Izmaylov et al., who found that transforming to the adiabatic representation must always be the last operation applied, though now we have extended this result to a time-dependent Hamiltonian. This paper and the proper derivation of the F-QCLE should lay the basis for further improvements of Floquet surface hopping.