# Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles

## Abstract

Efficient Monte Carlo algorithms are combined with the Quickstep energy routines of CP2K to develop a program that allows for Monte Carlo simulations in the canonical, isobaric-isothermal, and Gibbs ensembles using a first principles description of the physical system. Configurational-bias Monte Carlo techniques and pre-biasing using an inexpensive approximate potential are employed to increase the sampling efficiency and to reduce the frequency of expensive ab initio energy evaluations. The new Monte Carlo program has been validated through extensive comparison with molecular dynamics simulations using the programs CPMD and CP2K. Preliminary results for the vapor-liquid coexistence properties (T = 473 K) of water using the Becke-Lee-Yang-Parr exchange and correlation energy functionals, a triple-zeta valence basis set augmented with two sets of d-type or p-type polarization functions, and Goedecker-Teter-Hutter pseudopotentials are presented. The preliminary results indicate that this description of water leads to an underestimation of the saturated liquid density and heat of vaporization and, correspondingly, an overestimation of the saturated vapor pressure.

- Authors:

- Publication Date:

- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

- Sponsoring Org.:
- USDOE

- OSTI Identifier:
- 950086

- Report Number(s):
- UCRL-JRNL-208404

TRN: US200910%%66

- DOE Contract Number:
- W-7405-ENG-48

- Resource Type:
- Journal Article

- Journal Name:
- Computer Physics Communication, vol. 169, no. 1-3, April 1, 2005, pp. 8

- Additional Journal Information:
- Journal Volume: 169; Journal Issue: 1-3

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALGORITHMS; EFFICIENCY; ELECTRON CORRELATION; FUNCTIONALS; POLARIZATION; SAMPLING; VALENCE; VAPOR PRESSURE; VAPORIZATION HEAT; WATER

### Citation Formats

```
McGrath, M, Siepmann, J I, Kuo, I W, Mundy, C J, Vandevondele, J, Sprik, M, Hutter, J, Mohamed, F, Krack, M, and Parrinello, M.
```*Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles*. United States: N. p., 2004.
Web.

```
McGrath, M, Siepmann, J I, Kuo, I W, Mundy, C J, Vandevondele, J, Sprik, M, Hutter, J, Mohamed, F, Krack, M, & Parrinello, M.
```*Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles*. United States.

```
McGrath, M, Siepmann, J I, Kuo, I W, Mundy, C J, Vandevondele, J, Sprik, M, Hutter, J, Mohamed, F, Krack, M, and Parrinello, M. 2004.
"Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles". United States. https://www.osti.gov/servlets/purl/950086.
```

```
@article{osti_950086,
```

title = {Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles},

author = {McGrath, M and Siepmann, J I and Kuo, I W and Mundy, C J and Vandevondele, J and Sprik, M and Hutter, J and Mohamed, F and Krack, M and Parrinello, M},

abstractNote = {Efficient Monte Carlo algorithms are combined with the Quickstep energy routines of CP2K to develop a program that allows for Monte Carlo simulations in the canonical, isobaric-isothermal, and Gibbs ensembles using a first principles description of the physical system. Configurational-bias Monte Carlo techniques and pre-biasing using an inexpensive approximate potential are employed to increase the sampling efficiency and to reduce the frequency of expensive ab initio energy evaluations. The new Monte Carlo program has been validated through extensive comparison with molecular dynamics simulations using the programs CPMD and CP2K. Preliminary results for the vapor-liquid coexistence properties (T = 473 K) of water using the Becke-Lee-Yang-Parr exchange and correlation energy functionals, a triple-zeta valence basis set augmented with two sets of d-type or p-type polarization functions, and Goedecker-Teter-Hutter pseudopotentials are presented. The preliminary results indicate that this description of water leads to an underestimation of the saturated liquid density and heat of vaporization and, correspondingly, an overestimation of the saturated vapor pressure.},

doi = {},

url = {https://www.osti.gov/biblio/950086},
journal = {Computer Physics Communication, vol. 169, no. 1-3, April 1, 2005, pp. 8},

number = 1-3,

volume = 169,

place = {United States},

year = {2004},

month = {10}

}