Spin-Unrestricted Multi-Configuration Time-Dependent Hartree Fock Theory

Abstract

Based on spin-unrestricted hartree fock theory, we present the spin unrestricted multi-configuration time dependent hartree fock theory (UMCTDHF) to describe the electron correlation dynamics of systems interacting with laser field. The positive spin orbitals and the negative spin orbitals are propagated in their own subspace respectively. The spin orbital in the spin-down subspace acts with that in the spin-up subspace by the reduced density matrix and mean field operator. The ground energy is acquired by propagating the trial wave function in the imaginary time by using spin-restricted MCTDHF (RMCTDHF) and UMCTDHF respectively. Then the ionization probabilities and the electrons energies are calculated by using RMCTDHF and UMCTDHF when the laser field is present. The ionization probability calculated with UMCTDHF agrees with the previous theoretical reports very well. The UMCTDHF method is accurate and applicable for open shell system beyond the capability of the RMCTDHF method.