Heats of adsorption of methane, ethane, and propane in H-chabazite (Si/Al = 14.4) have been measured and entropies have been derived from adsorption isotherms. For these systems quantum chemical ab initio calculations of Gibbs free energies have been performed. The deviations from the experimental values for methane, ethane, and propane are below 3 kJ/mol for the enthalpy, and the Gibbs free energy. A hybrid high-level (MP2/CBS): low-level (DFT+dispersion) method is used to determine adsorption structures and energies. Vibrational entropies and thermal enthalpy contributions are obtained from vibrational partition functions for the DFT+dispersion potential energy surface. Anharmonic corrections have been evaluated for each normal mode separately. One-dimensional Schrodinger equations are solved for potentials obtained by (curvilinear) distortions of the normal modes using a representation in internal coordinates.

We extend the previously developed geometrical correction for the inter- and intramolecular basis set superposition error (gCP) to periodic density functional theory (DFT) calculations. We report gCP results compared to those from the standard Boys-Bernardi counterpoise correction scheme and large basis set calculations. The applicability of the method to molecular crystals as the main target is tested for the benchmark set X23. It consists of 23 noncovalently bound crystals as introduced by Johnson et al. (J. Chem. Phys. 2012, 137, 054103) and refined by Tkatchenko et al. (J. Chem. Phys. 2013, 139, 024705). In order to accurately describe long-range electron correlation effects, we use the standard atom-pairwise dispersion correction scheme DFT-D3. We show that a combination of DFT energies with small atom-centered basis sets, the D3 dispersion correction, and the gCP correction can accurately describe van der Waals and hydrogen-bonded crystals. Mean absolute deviations of the X23 sublimation energies can be reduced by more than 70% and 80% for the standard functionals PBE and B3LYP, respectively, to small residual mean absolute deviations of about 2 kcal/mol (corresponding to 13% of the average sublimation energy). As a further test, we compute the interlayer interaction of graphite for varying distances and obtain a good equilibrium distance and interaction energy of 6.75 Å and -43.0 meV/atom at the PBE-D3-gCP/SVP level. We fit the gCP scheme for a recently developed pob-TZVP solid-state basis set and obtain reasonable results for the X23 benchmark set and the potential energy curve for water adsorption on a nickel (110) surface.

The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide‐and‐conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction‐type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre‐exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude).

Hybrid MP2:DFT-D structure optimizations are performed at BSSE-free CBS-extrapolated potential energy surfaces for molecule–oxide surface interactions (BSSE, basis set superposition error; CBS, complete basis set limit). Subsequently single point MP2 calculations are performed to estimate the effects of increasing the basis set size in the CBS extrapolation and increasing the cluster model size. The resulting estimates of the periodic MP2 limit agree within 1 kJ/mol with Local MP2 calculations using periodic boundary conditions. Single point CCSD­(T) calculations are performed to determine ΔCC = CCSD­(T) – MP2 energy differences. The final hybrid MP2:DFT-D+ΔCC estimate for CO on the MgO(001) surface at low coverage, −21.2 ± 0.5 kJ/mol, is in close agreement with the reference energy derived from temperature-programmed desorption experiments, −20.6 ± 2.4 kJ/mol. For H2O on MgO(001), at limiting zero coverage, we predict an adsorption energy of −53.7 ± 4.2 kJ/mol which falls in the range of values, −55.8 ± 12.2 kJ/mol, derived from a high coverage low energy electron diffraction experiments and estimated lateral interactions.

A hybrid QM:QM method that combines MP2 as high-level method on cluster models with density functional theory (PBE+D2) as low-level method on periodic models is applied to adsorption of methane and ethane on the MgO(001) surface for which reliable experimental desorption enthalpies are available. Two coverages are considered, monolayer (every second Mg2+ ion occupied) and one quarter coverage (one of eight Mg2+ ions occupied). Structure optimizations are performed at the hybrid MP2:(PBE+D2) level, with the MP2 energies and forces counterpoise corrected for basis set superposition error and extrapolated to the complete basis set limit. For the MP2 calculations on the adsorbate monolayer a two-body expansion of the lateral molecule-molecule interactions is applied. Higher order correlation effects are evaluated at the hybrid MP2:(PBE+D2) equilibrium structures as coupled cluster [CCSD(T)] - MP2 differences adopting smaller basis sets. The final adsorption energies obtained for monolayer coverage are -14.0 ± 1.0 and -23.3 ± 0.6 kJ mol-1 for CH4·MgO(001) and C2H6·MgO(001), respectively. They agree within 1 kJ mol-1 - well within chemical accuracy limits - with reference energies of -15.0 ± 0.6 and -24.4 ± 0.6 kJ mol-1, respectively. The latter have been derived from measured desorption enthalpy barriers, taking zero-point vibrational energy (ZPVE) and thermal enthalpy contributions into account.