Ab initio Free Energy Calculations with Chemical Accuracy for Molecule-Surface Interactions

Atomistic understanding of heterogeneous catalysis as well as of storage and separation of energy-relevant gases in nanoporous materilas requires mechanical ab initio prediction of free energies for large periodic systems with chemical accuracy (4 kJ/mol). We have shown that this can be achieved by (i) use of hybrid high level - low level calculations combining accurate wave-functional theory calculations on the full (pseudo) periodic system, and (ii) calculating anharmonic vibrational energies in an affordable posed (1) to develop a robust and broadly applicable methodology that will be freely available to the community, taking the risk that the approximations we apply to calculate anharmonicities are not valid for all types of surface bonding and that a crucial technical step - curvilinear representation of normal modes - can not be made sufficiently automatic, (2) to built a data base of molecule-surface interactions for which agreement is achieved with experimental enthalpies and/or entropies and which are, thus, suitable for benchmarking approximate methods, and (3) to use this methodology to obtain kinetic and thermodynamic data for elementary steps in selected applications, e.g., catalysis by zeolites as well as gas storage and separation by metal-organic frameworks.

Principal Investigators
Sauer, Joachim Prof. Dr. rer. nat. Dr. h.c. (Details) (Theoretical Chemistry / Quantum Chemistry)

Duration of Project
Start date: 12/2015
End date: 06/2021

G. Piccini, M. Alessio, J. Sauer, Y. Zhi, Y. Liu, R. Kolvenbach, A. Jentys, J. A. Lercher, Accurate Adsorption Thermodynamics of Small Alkanes in Zeolites. Ab initio Theory and Experiment for H- Chabazite, J. Phys. Chem. C 119 (2015) 6128-6137.

G. Piccini, M. Alessio, J. Sauer, Ab initio calculation of rate constants for molecule - surface reactions with chemical accuracy, Angew. Chem., 128 (2016) 5321-5323. Angew. Chem., Int. Ed. 54 (2016) 5235-5237.

A. Kundu, G. Piccini, K. Sillar, J. Sauer Ab initio Prediction of Adsorption Isotherms for Small Molecules in Metal-Organic Frameworks, J. Am. Chem. Soc. 138 (2016) 14047-14056.

A. Kundu, K. Sillar, J. Sauer, Ab Initio Prediction of Adsorption Isotherms for Gas Mixtures by Grand Canonical Monte Carlo Simulations on a Lattice of Sites, J. Phys. Chem. Lett. 8 (2017) 2713-2718.

K. Sillar, A. Kundu, J. Sauer, Ab Initio Adsorption Isotherms for Molecules with Lateral Interactions: CO2 in Metal-Organic Framework, J. Phys. Chem. C 121 (2017) 12789-12799.

M. Alessio, F. Bischoff, J. Sauer, Chemically Accurate Adsorption Energies for Methane and Ethane Monolayers on the MgO(001) Surface, Phys. Chem. Chem. Phys. 20 (2018) 9760-9769.

G. Piccini, M. Alessio, J. Sauer, Ab initio study of methanol an ethanol adsorption on Brønsted sites in zeolite H-MFI, Phys. Chem. Chem. Phys. 20 (2018) 19964-19970.

M. Rybicki, J. Sauer, Ab initio prediction of Proton Exchange Barriers for Alkanes at Brønsted Sites of Zeolite H-MFI, J. Am. Chem. Soc. 140 (2018) 18151-18161.

M. Rybicki, J. Sauer, Acid Strength of Zeolitic Brønsted Sites - Dependence on Dielectric Properties, Catal. Today 323 (2019) 86-93.

M. Alessio, D. Usvyat, J. Sauer, Chemically Accurate Adsorption Energies: CO and H2O on the MgO(001) Surface, J. Chem. Theory Comput. 15 (2019) 1329-1344.

J. Sauer, Ab Initio Calculations for Molecule-Surface Interactions with Chemical Accuracy, Acc. Chem. Res. 52 (2019) 3502-3510.

A. Kundu, K. Sillar, J. Sauer, Predicting adsorption selectivities from pure gas isotherms for gas mixtures in metal-organic frameworks, Chem. Sci. 11 (2019) 643 - 655.

Last updated on 2021-04-01 at 17:44