Liouville-von Neumann molecular dynamics

Jacek Jakowski, Keiji Morokuma

Research output: Contribution to journalArticlepeer-review

48 Scopus citations

Abstract

We present a novel first principles molecular dynamics scheme, called Liouville-von Neumann molecular dynamics, based on Liouville-von Neumann equation for density matrices propagation and Magnus expansion of the time-evolution operator. The scheme combines formally accurate quantum propagation of electrons represented via density matrices and a classical propagation of nuclei. The method requires a few iterations per each time step where the Fock operator is formed and von Neumann equation is integrated. The algorithm (a) is free of constraint and fictitious parameters, (b) avoids diagonalization of the Fock operator, and (c) can be used in the case of fractional occupation as in metallic systems. The algorithm is very stable, and has a very good conservation of energy even in cases when a good quality conventional Born-Oppenheimer molecular dynamics trajectories is difficult to obtain. Test simulations include initial phase of fullerene formation from gaseous C2 and retinal system.

Original languageEnglish
Article number224106
JournalJournal of Chemical Physics
Volume130
Issue number22
DOIs
StatePublished - 2009
Externally publishedYes

Funding

The present research was supported in part by a grant from AFOSR (No. FA9550-07-1-0395) and in part by a grant from Gaussian Inc. In this work we used SCC-DFTB program for formation of Fock operator implemented by G. Zheng. J.J. would like to gratefully acknowledge discussions with B. Schlegel, Xiaosong Li, G. Zheng, J. Tully, D. Marx, N. Doltsinis, and J. Hutter during the preparation of this manuscript.

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