Transition-state correlations for predicting thermochemistry of adsorbates and surface reactions

Estimating thermochemical properties from linear correlations may provide a pathway to circumvent expensive density functional theory (DFT) calculations for quantities such as pre-exponentials and temperature corrections to DFT energies. Here, we construct thermochemical scaling relations between C...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2023-03, Vol.25 (12), p.8412-8423
Main Authors: Kurdziel, Sophia J, Vlachos, Dionisios G
Format: Article
Language:English
Subjects:
Adsorbates
Alkanes
Correlation
Dehydrogenation
Density functional theory
Ethane
Functional groups
Hydrogenolysis
Linearity
Mathematical analysis
Metal surfaces
Propane
Reaction mechanisms
Surface reactions
Thermochemical properties
Thermochemistry
Transition metals
Vapor phases
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Summary:Estimating thermochemical properties from linear correlations may provide a pathway to circumvent expensive density functional theory (DFT) calculations for quantities such as pre-exponentials and temperature corrections to DFT energies. Here, we construct thermochemical scaling relations between C 1 -C 6 n -alkanes in the gas phase and adsorbed alkyl chains extending from several transition metal surfaces, and examine changes in the slope and fit between metals and adsorption sites. We subsequently add -OH, -NH 2 , C&z.dbd;O, and C&z.dbd;C functional groups to the C 1 -C 6 molecules and demonstrate strong linear correlations for thermochemistry across all species. We broaden the correlations to incorporate transition states of C 1 -C 6 n -alkane dehydrogenation reactions, where thermochemistry for computationally prohibitive transition-state calculations can be quickly assessed. Additionally, we rationalize the linearity of thermochemical correlations based on the composition of the homologous series and theoretical assessments. As an application of the correlations, we estimate pre-exponentials for elementary surface reactions of ethane and propane hydrogenolysis on Ru(0001), which is of relevance to plastic hydrogenolysis. Depending on kinetically important steps, entropic contributions may be necessary to include in certain reaction mechanisms; in contrasting examples, entropies are found to be relatively insignificant for ethane hydrogenolysis but pertinent for propane hydrogenolysis. Entropies of transition states for surface reactions may be estimated using gas-phase species or local minima using linear correlations developed from density functional theory.
ISSN:1463-9076
1463-9084
DOI:10.1039/d2cp04425k