UCL Discovery
UCL home » Library Services » Electronic resources » UCL Discovery

Structural and dynamical properties predicted by reactive force fields simulations for four common pure fluids at liquid and gaseous non-reactive conditions

Le, TTB; Striolo, A; Cole, DR; (2018) Structural and dynamical properties predicted by reactive force fields simulations for four common pure fluids at liquid and gaseous non-reactive conditions. Molecular Simulation , 44 (10) pp. 826-839. 10.1080/08927022.2018.1455005. Green open access

[thumbnail of Le_Structural_dynamical_properties.pdf]
Preview
Text
Le_Structural_dynamical_properties.pdf - Accepted Version

Download (1MB) | Preview

Abstract

Four common pure fluids were chosen to elucidate the reliability of reactive force fields in estimating bulk properties of selected molecular systems: CH 4 , H 2 O, CO 2 and H 2 . The pure fluids are not expected to undergo chemical reactions at the conditions chosen for these simulations. The ‘combustion’ ReaxFF was chosen as reactive force field. In the case of water, we also considered the ‘aqueous’ ReaxFF model. The results were compared to data obtained implementing popular classic force fields. In the gas phase, it was found that simulations conducted using the ‘combustion’ ReaxFF formalism yield structural properties in reasonable good agreement with classic simulations for CO 2 and H 2 , but not for CH 4 and H 2 O. In the liquid phase, ‘combustion’ ReaxFF simulations reproduce reasonably well the structure obtained from classic simulations for CH 4 , degrade for CO 2 and H 2 , and are rather poor for H 2 O. In the gas phase, the simulation results are compared to experimental second virial coefficient data. The ‘combustion’ ReaxFF simulations yield second virial coefficients that are not sufficiently negative for CH 4 and CO 2 , and slightly too negative for H 2 . The ‘combustion’ ReaxFF parameterisation induces too strong an effective attraction between water molecules, while the ‘aqueous’ ReaxFF yields a second virial coefficient that is in reasonable agreement with experiments. The ‘combustion’ ReaxFF parameterisation yields acceptable self-diffusion coefficients for gas-phase properties of CH 4 , CO 2 and H 2 . In the liquid phase, the results are good for CO 2 , while the self-diffusion coefficient predicted for liquid CH 4 is slower, and that predicted for liquid H 2 is about nine times faster than those expected based on classic simulations. The ‘aqueous’ ReaxFF parameterisation yields good results for both the structure and the diffusion of both liquid and vapour water.

Type: Article
Title: Structural and dynamical properties predicted by reactive force fields simulations for four common pure fluids at liquid and gaseous non-reactive conditions
Open access status: An open access version is available from UCL Discovery
DOI: 10.1080/08927022.2018.1455005
Publisher version: https://doi.org/10.1080/08927022.2018.1455005
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
Keywords: Self-diffusion coefficient, radial distribution function, bulk fluids
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering
URI: https://discovery.ucl.ac.uk/id/eprint/10048230
Downloads since deposit
349Downloads
Download activity - last month
Download activity - last 12 months
Downloads by country - last 12 months

Archive Staff Only

View Item View Item