Influence of dispersion interactions on the adsorption of NTCDA on Ag(110)

Document Type : Research Article

Authors

1 Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran

2 Institut für Physik, Technische Universität Chemnitz, D-09107 Chemnitz, Germany

3 Leibniz Institut für Polymerforschung, Hohe Straße 6, 01069 Dresden, Germany

10.22091/jaem.2023.9638.1004

Abstract

In the present work, the adsorption of 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTCDA) on a (110)-oriented silver substrate is investigated with second-order Møller-Plesset perturbation theory (MP2). The metal surface was modeled using rigid silver clusters of finite size, allowing to test of the convergence of the optimized adsorbate geometry as a function of the size of the metal cluster. The geometry is converged for most of the substrate models, but the adsorption energy depends more severely on the size of the metal cluster. The dispersion interaction included in MP2 gives a nearly flat adsorbate geometry, whereas its lack of density functional theory (DFT) results in a bent geometry arising from strong silver-oxygen interactions and overlap repulsion in the central part of the molecule. Irrespective of the method used, the carboxylic oxygens interact more strongly with the substrate than the anhydride oxygen atoms, so that their height above the topmost substrate layer is significantly smaller. On the largest silver clusters used, MP2 converges to a height of 2.57 Å for the carbon atoms, somewhat closer than a value of 2.68 Å obtained with MP2 for the similar but larger molecule PTCDA on the same substrate orientation. 

Keywords

Main Subjects

In this work, we have applied MP2 and DFT calculations to study the adsorption of NTCDA on a (110)-oriented silver surface. To model the adsorbate geometry, we have used rigid Ag clusters of different sizes. Silver clusters consisting of at least 22 atoms gave MP2 adsorbate geometries agreeing within height variations of less than 0.09 Å between different substrate models. Rather strong bonds between carboxylic oxygens and the substrate atoms underneath define the preferential adsorption site and induce specific height variations within the functional groups. In the central naphthalene region, our calculation accounting for a partial compensation between overlap repulsion and attractive dispersion interaction predicts an essentially flat adsorption geometry, whereas the lack of dispersion interaction in DFT results in a bent adsorbate geometry where the central part of the molecule is repelled from the substrate. Dispersion-corrected DFT accounting for pairwise interatomic dispersion potentials still gives a significantly bent adsorbate geometry. From the present results and previous studies of PTCDA adsorbates, we consider wave function-based dispersion interactions included at the MP2 level to be the most adequate approach for investigations of aromatic adsorbates on noble metals

Table 3. Binding energy of the core levels in NTCDA:  multilayer,  monolayer chemisorbed on Ag(111), and monolayer chemisorbed on Ag(110). All calculations are performed with B3LYP/def-SV(P). The geometry of the free molecule is optimized with B3LYP/def-SV(P), and NTCDA chemisorbed to Ag(110) corresponds to the MP2 geometry on Ag34(9,16,9),  scanned to the minimum of the BSSE-CP corrected PES. O1 and O2 represent carboxylic and anhydride oxygens. * Scaled calculated values are obtained using a scaling factor of 1.0235.

 

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