First principles theory of organic molecules on metal surfaces : formate, 3-thiophene-carboxylate and glycinate on Cu(110)

In the following, we summarize the main contributions of the present work for the understanding of the interaction between organic molecules with the Cu(110) surface by performing ab initio calculations. We have used the program package EStCoMPP (Electronic Structure Code for Material Properties and Processes) that is based on density functional theory, pseudopotential and supercell approaches. In order to describe accurately the molecule-metal surface interaction we have implemented the generalized gradient approximation (GGA) ([PW92], [PBE96-98]) for the exchange-correlation functional in the EStCoMPP-package. This includes two atomic generation programs (one used to generate norm-conserving type pseudopotentials of the Kleinman-Bylander form (KB) [BHS82, KB82], and the other used to generate non-norm-conserving type pseudopotentials using the projectoraugmented plane wave method (PAW) [Blö94, Kro01]) and the main program used in the solid-state calculations. In the main program the gradient-corrected exchange-correlation functional can be evaluated using two schemes: a traditional scheme$^{1}$ [PBE92, PBE96-97] and a new scheme proposed by White and Bird$^{2}$ [WB94]. In addition, a new scheme to calculate the partial core-correction charge3 (PCC) in realspace has been implemented. A series of pseudopotentials have been generated: Si, Cd, S, Ti, O, Cu, N, C, Pt, Ga (PAW-type) and Sr (KB-type). Several calculations including various bulk crystals (Si-cubic, Cd-hex, CdO-cubic, CdS-cubic, CdS-hex, SrO, TiO-cubic, SrTiO$_{3}$-sc, SiO$_{2}$-hex, TiN-cubic, Pt-cubic, PtGa$_{2}$-cubic, Cu-cubic) and molecules (SiH$_{3}$, NO, CO, CN, O$_{2}$, NH$_{3}$, CH$_{4}$, formate, 3-thiophene carboxylate and glycinate) have been performed in order to verify the accuracy of our generated pseudopotentials, and the approximations to the exchange-correlation functional. All tests show that our results are in good agreement with experimental and theoretical data in the literature