J Chem Theory Comput. 2014 Jun 10;10(6):2479-87. doi: 10.1021/ct500291x. Epub 2014 May 22.
Journal of chemical theory and computation
GiovanniMaria Piccini, Joachim Sauer
PMID: 26580768 DOI: 10.1021/ct500291x
The effect of anharmonic corrections to the vibrational energies of extended systems is explored. Particular attention is paid to the thermodynamics of adsorption of small molecules on catalytically relevant systems typically affected by anharmonicity. The implemented scheme obtains one-dimensional anharmonic model potentials by distorting the equilibrium structure along the normal modes using both rectilinear (Cartesian) or curvilinear (internal) representations. Only in the latter case, the modes are decoupled also at higher order of the potential and the thermodynamic functions change in the expected directions. The method is applied to calculate ab initio enthalpies, entropies, and Gibbs free energies for the adsorption of methane in acidic chabazite (H-CHA) and on MgO(001) surface. The values obtained for the adsorption of methane in H-CHA (273.15 K, 0.1 MPa, θ = 0.5) are ΔH = -19.3, -TΔS = 11.9, and ΔG = -7.5 kJ/mol. For methane on the MgO(001) (47 K, 1.3 × 10(-14) MPa, θ = 1) ΔH = -14.4, -TΔS = 16.6, and ΔG = 2.1 kJ/mol are obtained. The calculated desorption temperature is 44 K, and the desorption prefactor is 4.26 × 10(12) s(-1). All calculated results agree within chemical accuracy limits with experimental data.
