Communication: Thermodynamics of water modeled using ab initio simulations

Valéry Weber; D. Asthagiri

doi:10.1063/1.3499315

Communication: Thermodynamics of water modeled using ab initio simulations

Valéry Weber, D. Asthagiri

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

Abstract

We regularize the potential distribution framework to calculate the excess free energy of liquid water simulated with the BLYP-D density functional. Assuming classical statistical mechanical simulations at 350 K model the liquid at 298 K, the calculated free energy is found in fair agreement with experiments, but the excess internal energy and hence also the excess entropy are not. The utility of thermodynamic characterization in understanding the role of high temperatures to mimic nuclear quantum effects and in evaluating ab initio simulations is noted.

Original language	English
Article number	141101
Journal	Journal of Chemical Physics
Volume	133
Issue number	14
DOIs	https://doi.org/10.1063/1.3499315
State	Published - Oct 14 2010
Externally published	Yes

Funding

The authors warmly thank Claude Daul (University of Fribourg) for computer resources. D.A. thanks the donors of the American Chemical Society Petroleum Research Fund for the financial support. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. .

Funders	Funder number
U.S. Department of Energy
Office of Science
American Chemical Society Petroleum Research Fund

Access to Document

10.1063/1.3499315

Cite this

@article{97f95984b7834fbead1753ea2551d76b,

title = "Communication: Thermodynamics of water modeled using ab initio simulations",

abstract = "We regularize the potential distribution framework to calculate the excess free energy of liquid water simulated with the BLYP-D density functional. Assuming classical statistical mechanical simulations at 350 K model the liquid at 298 K, the calculated free energy is found in fair agreement with experiments, but the excess internal energy and hence also the excess entropy are not. The utility of thermodynamic characterization in understanding the role of high temperatures to mimic nuclear quantum effects and in evaluating ab initio simulations is noted.",

author = "Val{\'e}ry Weber and D. Asthagiri",

year = "2010",

month = oct,

day = "14",

doi = "10.1063/1.3499315",

language = "English",

volume = "133",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

number = "14",

}

TY - JOUR

T1 - Communication

T2 - Thermodynamics of water modeled using ab initio simulations

AU - Weber, Valéry

AU - Asthagiri, D.

PY - 2010/10/14

Y1 - 2010/10/14

N2 - We regularize the potential distribution framework to calculate the excess free energy of liquid water simulated with the BLYP-D density functional. Assuming classical statistical mechanical simulations at 350 K model the liquid at 298 K, the calculated free energy is found in fair agreement with experiments, but the excess internal energy and hence also the excess entropy are not. The utility of thermodynamic characterization in understanding the role of high temperatures to mimic nuclear quantum effects and in evaluating ab initio simulations is noted.

AB - We regularize the potential distribution framework to calculate the excess free energy of liquid water simulated with the BLYP-D density functional. Assuming classical statistical mechanical simulations at 350 K model the liquid at 298 K, the calculated free energy is found in fair agreement with experiments, but the excess internal energy and hence also the excess entropy are not. The utility of thermodynamic characterization in understanding the role of high temperatures to mimic nuclear quantum effects and in evaluating ab initio simulations is noted.

UR - http://www.scopus.com/inward/record.url?scp=77958093256&partnerID=8YFLogxK

U2 - 10.1063/1.3499315

DO - 10.1063/1.3499315

M3 - Article

AN - SCOPUS:77958093256

SN - 0021-9606

VL - 133

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 14

M1 - 141101

ER -

Communication: Thermodynamics of water modeled using ab initio simulations

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this