Prediction of Transition-State Scaling Relationships and Universal Transition-State Vibrational and Entropic Correlations for Dehydrogenations

Kurdziel, Sophia J.; Lansford, Joshua L.; Vlachos, Dionisios G.

doi:10.1021/acs.jpcc.1c05425

Prediction of Transition-State Scaling Relationships and Universal Transition-State Vibrational and Entropic Correlations for Dehydrogenations

Journal Article · Fri Sep 03 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c05425· OSTI ID:2212401

Kurdziel, Sophia J. ^[1]; Lansford, Joshua L. ^[2]; ^[2]

University of Delaware, Newark, DE (United States); University of Delaware
University of Delaware, Newark, DE (United States)

Linear scaling relationships (LSRs) and Brønsted–Evans–Polanyi (BEP) or transition-state scaling (TSS) relations aid with the prediction of electronic energies. However, temperature effects and pre-exponentials are often taken as constants across metal surfaces or a homologous series. Vibrational scaling relationships (VSRs) offer a way to determine such parameters. Transition-state VSRs (TSVSRs) between local minima and transition states of AH_X (A = C, N, O) surface diffusions correlate with BEP relations and broaden to thermochemical property scaling. Using density functional theory, we extend TSVSRs to AHX dehydrogenation reactions on transition-metal surfaces, relating vibrational modes of local minima to transition states. We first predict the slopes of the TSS relations by incorporating bond angles using the Slater–Koster structure factors and hybridization through crystal orbital overlap population analysis and energy overlap integrals between adsorbates and metal surfaces. Additionally, we uncover universal thermochemical property scaling, enabling the estimation of entropies and temperature corrections to enthalpies across a homologous series. Here, we demonstrate both significant vibrational corrections in reactions with low intrinsic electronic barriers and considerable variation in the pre-exponential of a simple dehydrogenation reaction across metals and AH_X adsorbates.

View Accepted Manuscript (DOE)

Research Organization:: RAPID Manufacturing Institute, New York, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO)

Grant/Contract Number:: EE0007888

OSTI ID:: 2212401

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 36 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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