Bicanonical ab Initio Molecular Dynamics for Open Systems

Journal article

Publication Details

Author(s): Frenzel J, Meyer B, Marx D
Journal: Journal of Chemical Theory and Computation
Publication year: 2017
Volume: 13
Journal issue: 8
Pages range: 3455-3469
ISSN: 1549-9618
eISSN: 1549-9626


Performing ab initio molecular dynamics simulations of open systems, where the chemical potential rather than the number of both nuclei and electrons is fixed, still is a challenge. Here, drawing on bicanonical sampling ideas introduced two decades ago by Swope and Andersen [ J. Chem. Phys. 1995 , 102 , 2851 - 2863 ] to calculate chemical potentials of liquids and solids, an ab initio simulation technique is devised, which introduces a fictitious dynamics of two superimposed but otherwise independent periodic systems including full electronic structure, such that either the chemical potential or the average fractional particle number of a specific chemical species can be kept constant. As proof of concept, we demonstrate that solvation free energies can be computed from these bicanonical ab initio simulations upon directly superimposing pure bulk water and the respective aqueous solution being the two limiting systems. The method is useful in many circumstances, for instance for studying heterogeneous catalytic processes taking place on surfaces where the chemical potential of reactants rather than their number is controlled and opens a pathway toward ab initio simulations at constant electrochemical potential.

FAU Authors / FAU Editors

Meyer, Bernd Prof. Dr.
Professur für Computational Chemistry

Additional Organisation
Exzellenz-Cluster Engineering of Advanced Materials

External institutions
Ruhr-Universität Bochum (RUB)

How to cite

Frenzel, J., Meyer, B., & Marx, D. (2017). Bicanonical ab Initio Molecular Dynamics for Open Systems. Journal of Chemical Theory and Computation, 13(8), 3455-3469.

Frenzel, Johannes, Bernd Meyer, and Dominik Marx. "Bicanonical ab Initio Molecular Dynamics for Open Systems." Journal of Chemical Theory and Computation 13.8 (2017): 3455-3469.


Last updated on 2019-21-03 at 08:32