Diffusion Monte Carlo in Internal Coordinates

作者：Petit Andrew S; McCoy Anne B^*

来源：Journal of Physical Chemistry A, 2013, 117(32): 7009-7018.

DOI：10.1021/jp312710u

An internal coordinate extension of diffusion Monte Carlo (DMC) is described as a first step toward a generalized reduced-dimensional DMC approach. The method places no constraints on the choice of internal coordinates other than the requirement that they all be independent. Using H-3(+) and its isotopologues as model systems, the methodology is shown to be capable of successfully describing the ground state properties of molecules that undergo large amplitude, zero-point vibrational motions. Combining the approach developed here with the fixed-node approximation allows vibrationally excited states to be treated. Analysis of the ground state probability distribution is shown to provide important insights into the set of internal coordinates that are less strongly coupled and therefore more suitable for use as the nodal coordinates for the fixed-node DMC calculations. In particular, the curvilinear normal mode coordinates are found to provide reasonable nodal surfaces for the fundamentals of H2D+ and D2H+ despite both molecules being highly fluxional.

• 出版日期2013-8-15