| Autor: |
Yang, Li, Taylor, Ramona, de Jong, Wibe A., Hase, William L. |
| Zdroj: |
The Journal of Physical Chemistry - Part C; June 2011, Vol. 115 Issue: 25 p12403-12413, 11p |
| Abstrakt: |
A hierarchy of electronic structure calculations, scalings, and fittings were used to develop an analytic intermolecular potential for dimethyl methylphosphonate (DMMP) interacting with the TiO2rutile (110) surface. The MP2/aug-cc-pVDZ (6-311+G** for Ti) level of theory, with basis set superposition error (BSSE) corrections, was used to calculate multiple intermolecular potential curves between TiO5H6as a model for the Ti and O atoms of the TiO2surface, and CH3OH and OP(CH3)(OH)2as models for different types of atoms comprising DMMP. Each intermolecular potential energy emphasized a particular atom–atom interaction, and the curves were fit simultaneously by a sum of two-body potentials between the atoms of the two interacting molecules. The resulting analytic intermolecular potential gives DMMP/TiO5H6potential curves in excellent agreement with those calculated using MP2/aug-cc-pVDZ (6-311+G** for Ti) theory. MP2 theory with the smaller basis set, 6-31++G** (6-31G** for Ti), gives DMMP/TiO5H6potential energy curves similar to those found using MP2/aug-cc-pVDZ (6-311+G** for Ti), suggesting the smaller basis set may be used to describe DMMP interactions with larger cluster models of the TiO2surface. The TiO5H6cluster does not model either the 6-fold coordinated Ti atoms or the bridging O atoms of the TiO2(110) surface, and to also model these atoms MP2/6-31++G** (6-31G** for Ti) theory was used to calculate potential energy curves for DMMP interacting with the larger Ti3O13H14cluster and much large cluster Ti11O40H36cluster. The two-body potential energy curves for DMMP/TiO5H6were scaled to fit both the DMMP/Ti3O13H14and DMMP/Ti11O40H36potential energy curves. The resulting parameters for the 5- and 6-fold coordinated Ti atoms and bridging and bulk O atoms were used to develop an analytic intermolecular potential for DMMP interacting with rutile TiO2(110). |
| Databáze: |
Supplemental Index |
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