title: A practical method to avoid zero-point leak in molecular dynamics calculations: application to the water dimer.
abstract: We report the implementation of a previously suggested method to constrain a molecular system to have mode-specific vibrational energy greater than or equal to the zero-point energy in quasiclassical trajectory calculations [J. M. Bowman et al., J. Chem. Phys. 91, 2859 (1989); W. H. Miller et al., J. Chem. Phys. 91, 2863 (1989)]. The implementation is made practical by using a technique described recently [G. Czako and J. M. Bowman, J. Chem. Phys. 131, 244302 (2009)], where a normal-mode analysis is performed during the course of a trajectory and which gives only real-valued frequencies. The method is applied to the water dimer, where its effectiveness is shown by computing mode energies as a function of integration time. Radial distribution functions are also calculated using constrained quasiclassical and standard classical molecular dynamics at low temperature and at 300 K and compared to rigorous quantum path integral calculations.
authors.affiliation: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA. czako@chem.elte.hu
authors.forename: Gábor
authors.initials: G
authors.lastname: Czakó
authors.forename: Alexey L
authors.initials: AL
authors.lastname: Kaledin
authors.forename: Joel M
authors.initials: JM
authors.lastname: Bowman