An ab initio path integral Monte Carlo simulation method for molecules and clusters: application to Li_4 and Li_5^+

Details An ab initio path integral Monte Carlo simulation method for molecules and clusters: application to Li_4 and Li_5^+ An ab initio path integral Monte Carlo simulation method for molecules and clusters: application to Li_4 and Li_5^+

1998-02-11

arxiv.org/abs/physics/9802020v1

Physics

Computational Physics

11 text pages, 7 figures, to be published in J. Chem. Phys

Scientific paper

10.1063/1.476331

A novel method for simulating the statistical mechanics of molecular systems in which both nuclear and electronic degrees of freedom are treated quantum mechanically is presented. The scheme combines a path integral description of the nuclear variables with a first-principles adiabatic description of the electronic structure. The electronic problem is solved for the ground state within a density functional approach, with the electronic orbitals expanded in a localized (Gaussian) basis set. The discretized path integral is computed by a Metropolis Monte Carlo sampling technique on the normal modes of the isomorphic ring-polymer. An effective short-time action correct to order $\tau^4$ is used. The validity and performance of the method are tested in two small Lithium clusters, namely Li$_4$ and Li$_5^+$. Structural and electronic properties computed within this fully quantum-mechanical scheme are presented and compared to those obtained within the classical nuclei approximation. Quantum delocalization effects are significant but tunneling turns out to be irrelevant at low temperatures.

Affiliated with

Also associated with

No associations

Rating

An ab initio path integral Monte Carlo simulation method for molecules and clusters: application to Li_4 and Li_5^+ does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.

If you have personal experience with An ab initio path integral Monte Carlo simulation method for molecules and clusters: application to Li_4 and Li_5^+, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and An ab initio path integral Monte Carlo simulation method for molecules and clusters: application to Li_4 and Li_5^+ will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFWR-SCP-O-522116