Path-integral virial estimator based on the scaling of fluctuation coordinates: Application to quantum clusters with fourth-order propagators
10.1063/1.2013257
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

We first show that a simple scaling of fluctuation coordinates defined in terms of a given reference point gives the conventional virial estimator in discretized path integral, where different choices of the reference point lead to different forms of the estimator (e.g., centroid virial). The merit of this procedure is that it allows a finite-difference evaluation of the virial estimator with respect to temperature, which totally avoids the need of higher-order potential derivatives. We apply this procedure to energy and heat-capacity calculations of the (H2)22 and Ne13 clusters at low temperature using the fourth-order Takahashi-Imada [J. Phys. Soc. Jpn. 53, 3765 (1984)] and Suzuki [Phys. Lett. A 201, 425 (1995)] propagators. This type of calculation requires up to third-order potential derivatives if analytical virial estimators are used, but in practice only first-order derivatives suffice by virtue of the finite-difference scheme above. From the application to quantum clusters, we find that the fourth-order propagators do improve upon the primitive approximation, and that the choice of the reference point plays a vital role in reducing the variance of the virial estimator.

Bibliography

Yamamoto, T. M. (2005). Path-integral virial estimator based on the scaling of fluctuation coordinates: Application to quantum clusters with fourth-order propagators. The Journal of Chemical Physics, 123(10).

Authors 1
  1. Takeshi M. Yamamoto (first)
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Dates
Type When
Created 19 years, 11 months ago (Sept. 7, 2005, 6:06 p.m.)
Deposited 2 years ago (July 30, 2023, 10:58 p.m.)
Indexed 1 month ago (July 30, 2025, 6:46 a.m.)
Issued 19 years, 11 months ago (Sept. 8, 2005)
Published 19 years, 11 months ago (Sept. 8, 2005)
Published Online 19 years, 11 months ago (Sept. 9, 2005)
Published Print 19 years, 11 months ago (Sept. 8, 2005)
Funders 0

None

@article{Yamamoto_2005, title={Path-integral virial estimator based on the scaling of fluctuation coordinates: Application to quantum clusters with fourth-order propagators}, volume={123}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.2013257}, DOI={10.1063/1.2013257}, number={10}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Yamamoto, Takeshi M.}, year={2005}, month=sep }