TY  - JOUR
A1  - Heiden, Sophia
A1  - Usvyat, Denis
A1  - Saalfrank, Peter
T1  - Theoretical Surface Science Beyond Gradient-Corrected Density Functional Theory
BT  - Water at alpha-Al2O3(0001) as a Case Study
JF  - The journal of physical chemistry : C, Nanomaterials and interfaces
N2  - The quantum chemical description of the adsorption, vibrations, and reactions of molecules at periodic solid surfaces is frequently based on a methodological "standard model": density functional theory (DFT) in the generalized gradient approximation (GGA), using plane wave bases and three-dimensional supercells. Although the computationally efficient GGA functionals can be very successful, cases are known where they do not perform so well. Most importantly, activation energies for chemical reactions are typically underestimated, with the consequence of computed reaction rates being too large. In this work, we consider a well-studied model system: water or water fragments adsorbed on an Al-terminated alpha-Al2O3(0001) surface as a test bed for studying the performance of electronic structure methods, both from DFT and wave function theory. On the DFT side, we employ two GGA exchange correlation functionals: PW91 and PBE with and without dispersion corrections, whose results are then compared to those of hybrid functionals B3LYP and HSE06. Further, we follow a periodic wave function approach in the form of local second-order Moller-Plesset perturbation theory, LMP2, on a Hartree-Fock reference. En route, we address issues arising from the choice of the basis set. The key findings of our study are as follows: (i) DFT-GGA adsorption energies are in reasonable agreement with both hybrid-DFT and LMP2 values. In particular, the deviations between the relative energies, corresponding to different adsorption structures, are in the range of the error due to missing dispersion corrections or the basis set error. (ii) Harmonic DFT-GGA vibrational frequencies for oxygen hydrogen stretch modes are by several tens of wavenumbers red-shifted compared to corresponding hybrid-DFT values. The latter are in much better agreement with recent experimental data. (iii) The activation energy for a hydrogen diffusion reaction is grossly underestimated by GGA compared to hybrid-DFT or LMP2, which in turn are quite comparable.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpcc.9b00407
SN  - 1932-7447
VL  - 123
IS  - 11
SP  - 6675
EP  - 6684
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - GEN
A1  - Halibasic, Emina
A1  - Fuerst, Elisabeth
A1  - Heiden, Denis
A1  - Japtok, Lukasz
A1  - Diesner, Susanne C.
A1  - Hillebrand, P.
A1  - Trauner, Michael
A1  - Kleuser, Burkhard
A1  - Kazemi-Shirazi, Lili
A1  - Untersmayr, Eva
T1  - Significantly reduced plasma levels of the bioactive sphingolipid S1P in lung transplanted cystic fibrosis patients are associated with gastrointestinal symptoms
T2  - Allergy
Y1  - 2017
SN  - 0105-4538
SN  - 1398-9995
VL  - 72
IS  - S103
SP  - 195
EP  - 195
PB  - Wiley
CY  - Hoboken
ER  -