Configuration Space Integration for Adsorbate Partition Functions: The Effect of Anharmonicity on the Thermophysical Properties of CO–Pt(111) and CH3OH–Cu(111)

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

doi:10.1021/acscatal.2c04246

Configuration Space Integration for Adsorbate Partition Functions: The Effect of Anharmonicity on the Thermophysical Properties of CO–Pt(111) and CH₃OH–Cu(111)

Journal Article · Thu Dec 08 23:00:00 EST 2022 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.2c04246· OSTI ID:2217020

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

Brown University, Providence, RI (United States)
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

A method for computing anharmonic thermophysical properties for adsorbates on metal surfaces has been extended to include libration, or frustrated rotation. Classical phase space integration is used with Monte Carlo sampling of the configuration space to obtain the partition function of CO on Pt(111) and CH₃OH on Cu(111). A minima-preserving neural network potential energy surrogate is used within the integration routines. Direct state counting using discrete variable representation is used to benchmark the results. We find that the phase space integration approach is in excellent agreement with the direct state counting results. Comparison with standard models such as the harmonic oscillator indicates that anharmonicity contributes significantly to the thermodynamic properties of CH₃OH on Cu(111). We find that there is also a considerable difference between the harmonic oscillator and phase space integration for CO on Pt(111), although the discrepancy can largely be attributed to the presence of multiple binding sites within the unit cell. We demonstrate that a multisite harmonic oscillator model might be sufficient for CO-Pt(111). A more thorough description of the potential energy surface, which can be achieved with phase space integration, is necessary for weakly bound adsorbates such as CH₃OH. In conclusion, the thermophysical properties were used to calculate free energies of adsorption on the respective metals, and subsequently the equilibrium constants and Langmuir isotherms in relevant temperature ranges. The results show that the choice of model to obtain partition functions greatly affects the resulting surface coverages in kinetic models.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

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

OSTI ID:: 2217020

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 1 Vol. 13; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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