PROJECTS

Ab initio correlated electron dynamics with the Multi-Configuration
(explicitly) Time-Dependent Hartree-Fock method

PRINCIPAL INVESTIGATOR

Prof. Dr. Peter Saalfrank Universität Potsdam Institut für Chemie Karl-Liebknecht-Straße 24/25 14476 Potsdam-Golm Germany 0331/9775232 0331/9775058 petsaal@rz.uni-potsdam.de www: Homepage

TOGETHER WITH

PROJECT RESEARCH ASSISTANT

ABSTRACT

In the first and early second periods of this project the Multi-Configuration Time-Dependent Hartree-Fock (MCTDHF) method was implemented and tested for one-dimensional model problems. Meanwhile, MCTDHF was realized in a Gaussian atomic orbital basis, allowing us to treat the correlated, manyelectron dynamics in three-dimensional molecular systems in real or imaginary time. The systematic convergence between the two limiting cases of MCTDHF, Hartree Fock and Full Configuration Interaction (FCI), has been demonstrated for small molecules. The TD-FCI limit has also been reached for a benchmark problem (short-pulse excitation of H₂), using the alternative TD-CI method. In the final project period, several methodical improvements / extensions will be made for MCTDHF (frozen core approximation, effective core potential implementation, optical potentials), but the focus is on applications: (i) The creation of electronic wavepackets in lithium hydride with laser pulses, (ii) the excitation and relaxation of electronic excitations in small sodium clusters, (iii) the calculation of vertical excitation energies and excited-state properties of molecules, and (iv) the charge migration in molecules after sudden electron or hole attachment.