Adsorbate Partition Functions via Phase Space Integration: Quantifying the Effect of Translational Anharmonicity on Thermodynamic Properties

Blöndal, Katrín; Sargsyan, Khachik; Bross, David H.; Ruscic, Branko; Goldsmith, C. Franklin

doi:10.1021/acs.jpcc.1c04009

Adsorbate Partition Functions via Phase Space Integration: Quantifying the Effect of Translational Anharmonicity on Thermodynamic Properties

Journal Article · Thu Sep 09 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c04009· OSTI ID:1823111

^[1]; Sargsyan, Khachik ^[2]; ^[3]; ^[3]; ^[1]

Brown Univ., Providence, RI (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

A new method for computing anharmonic thermophysical properties for adsorbates on metal surfaces is presented. Classical Monte Carlo phase space integration is performed to calculate the partition function for the motion of a hydrogen atom on Cu(111). Here, a minima-preserving neural network potential energy surface is used within the integration routine. Two different sampling schema for generating the training data are presented, and two different density functionals are used. The results are benchmarked against direct state counting results by using discrete variable representation. The phase space integration results are in excellent quantitative agreement with the benchmark results. Additionally, both the discrete variable representation and the phase space integration results confirm that the motion of H on Cu(111) is highly anharmonic. The results were applied to calculate the free energy of dissociative adsorption of H₂ and the resulting Langmuir isotherms at 400, 800, and 1200 K in a partial pressure range of 0–1 bar. It shows that the anharmonic effects lead to significantly higher predicted surface site fractions of hydrogen.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; NA0003525

OSTI ID:: 1823111

Alternate ID(s):: OSTI ID: 1877132

Report Number(s):: SAND2022-8487J; 167653

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 37 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Adsorbate Partition Functions via Phase Space Integration: Quantifying the Effect of Translational Anharmonicity on Thermodynamic Properties

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