PROJECTS

Ab initio electron dynamics with the multi-configuration (explicitly) time-dependent Hartree-Fock (MCTDHF) method

PRINCIPAL INVESTIGATOR

Prof. Dr. Peter Saalfrank Universität Potsdam Theoretische Chemie Karl-Liebknecht-Straße 24-25 D-14476 Golm +49(0)331-977-5232 petsaal@rz.uni-potsdam.de

TOGETHER WITH

ABSTRACT

The goal of this project is to implement and test the Multi-Configuration Time-Dependent Hartree-Fock (MCTDHF) method in its explicitly time dependent form. The method expands a multi-electron wave function into a sum of Slater determinants, with variationally optimized coefficient vector and single-particle-functions (SPFs). The method has been used up to now only in the linear response regime, so that a considerable amount of work is necessary for implementation and testing as well as comparison to other methods, such as Time-Dependent Hartree-Fock (TDHF) or Time-Dependent Configuration Interaction (TDCI). We will then apply the method to study optical properties and the electron relaxation dynamics of atoms and metal clusters. We hope to be able to determine the linewidths in photoabsorption spectra of clusters, and the corresponding lifetimes of excited states, from first principles. Also, the observation of the relaxation of a multi-electron system became possible recently with a sub-femtosecond resolution. We want to simulate these pump-probe experiments, which gives insight into different possible relaxation pathways as well as the role and nature of the transient states involved.

PUBLICATIONS

P. Krause, T. Klamroth, P. Saalfrank,
Time-dependent configuration interaction calculations of laser-pulse
driven many electron dynamics: Controlled dipole switching in lithium cyanide
J. Chem. Phys. submitted.

M. Nest, T. Klamroth,
Correlated many electron dynamics: Application to inelastic electron
scattering at a metal film
Phys. Rev. A, accepted.

P. Saalfrank, T. Klamroth, C. Huber, P. Krause,
Laser-driven electron dynamics at interfaces
Isr. J. Chem. (2005) (in press).

M. Nest, T. Klamroth, P. Saalfrank,
The multiconfiguration time-dependent Hartree-Fock method for
quantum chemical calculations
J. Chem. Phys. 122, 124102 (2005).