Non-polarizable empirical potentials have been proven to be incapable of capturing the mixing of methane–water mixtures at elevated pressures. Although density functional theory-based ab initio simulations may circumvent this discrepancy, they are limited in terms of the relevant time and length scales associated with mixing phenomena. Here, we show that the many-body MB-nrg potential, designed to reproduce methane–water interactions with coupled cluster accuracy, successfully captures this phenomenon up to 3 GPa and 500 K with varying methane concentrations. Two-phase simulations and long time scales that are required to fully capture the mixing, affordable due to the speed and accuracy of the MBX software, are assessed. Constructing the methane–water equation of state across the phase diagram shows that the stable mixtures are denser than the sum of their parts at a given pressure and temperature. We find that many-body polarization plays a central role, enhancing the induced dipole moments of methane by 0.20 D during mixing under pressure. Overall, the mixed system adopts a denser state, which involves a significant enthalpic driving force as elucidated by a systematic many-body energy decomposition analysis.
Skip Nav Destination
CHORUS
Article navigation
21 May 2022
Research Article|
May 18 2022
The behavior of methane–water mixtures under elevated pressures from simulations using many-body potentials
Victor Naden Robinson
;
Victor Naden Robinson
1
The ‘Abdus Salam’ International Centre for Theoretical Physics
, I-34151 Trieste, Italy
Search for other works by this author on:
Raja Ghosh;
Raja Ghosh
2
Department of Chemistry and Biochemistry, University of California, San Diego
, La Jolla, California 92093, USA
Search for other works by this author on:
Colin K. Egan;
Colin K. Egan
1
The ‘Abdus Salam’ International Centre for Theoretical Physics
, I-34151 Trieste, Italy
Search for other works by this author on:
Marc Riera
;
Marc Riera
2
Department of Chemistry and Biochemistry, University of California, San Diego
, La Jolla, California 92093, USA
Search for other works by this author on:
Christopher Knight
;
Christopher Knight
3
Computational Science Division, Argonne National Laboratory
, 9700 South Cass Avenue, Lemont, Illinois 60439, USA
Search for other works by this author on:
Francesco Paesani
;
Francesco Paesani
a)
2
Department of Chemistry and Biochemistry, University of California, San Diego
, La Jolla, California 92093, USA
4
Materials Science and Engineering, University of California San Diego
, La Jolla, California 92093, USA
5
San Diego Supercomputer Center, University of California San Diego
, La Jolla, California 92093, USA
Search for other works by this author on:
Ali Hassanali
Ali Hassanali
b)
1
The ‘Abdus Salam’ International Centre for Theoretical Physics
, I-34151 Trieste, Italy
b)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
a)
Electronic mail: [email protected]
b)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 156, 194504 (2022)
Article history
Received:
February 28 2022
Accepted:
April 25 2022
Citation
Victor Naden Robinson, Raja Ghosh, Colin K. Egan, Marc Riera, Christopher Knight, Francesco Paesani, Ali Hassanali; The behavior of methane–water mixtures under elevated pressures from simulations using many-body potentials. J. Chem. Phys. 21 May 2022; 156 (19): 194504. https://doi.org/10.1063/5.0089773
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Freezing point depression of salt aqueous solutions using the Madrid-2019 model
Cintia P. Lamas, Carlos Vega, et al.
Related Content
Can the AMOEBA forcefield be used for high pressure simulations? The extreme case of methane and water
J. Chem. Phys. (August 2024)
How to determine solubility in binary mixtures from neutron scattering data: The case of methane and water
J. Chem. Phys. (February 2022)
Modulating magnetism of ZnO:C with vacancy and substitution
J. Appl. Phys. (December 2011)
Aqueous solution chemistry in silico and the role of data-driven approaches
Chem. Phys. Rev. (June 2024)
Communication: Physical origins of ionization potential shifts in mixed carboxylic acids and water complexes
J. Chem. Phys. (August 2016)