Using theoretical descriptors to model solvent effects in the isomerization ofcis-stilbene
| Autor: | Michael C. Zerner, Krassimir K. Stavrev, Alfred H. Lowrey, Toomas Tamm, R. Andrew McGill, Andrew P. Baronavski, Jane K. Rice, Jeffrey C. Owrutsky |
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| Rok vydání: | 1996 |
| Předmět: |
Physics::Biological Physics
Quantitative Biology::Biomolecules Photoisomerization Chemistry Solvation Thermodynamics Condensed Matter Physics Polarizable continuum model Atomic and Molecular Physics and Optics Condensed Matter::Soft Condensed Matter Solvent Solvation shell Computational chemistry Polarizability Physics::Atomic and Molecular Clusters Physics::Chemical Physics Physical and Theoretical Chemistry Solvent effects Isomerization |
| Zdroj: | International Journal of Quantum Chemistry. 60:1595-1606 |
| ISSN: | 1097-461X 0020-7608 |
| DOI: | 10.1002/(sici)1097-461x(1996)60:7<1595::aid-qua41>3.0.co;2-z |
| Popis: | Experimental observations of the photoinduced excited-state lifetime of cis-stilbene have shown a distinct dependence on solvation processes. The rate of decay, dominated by a cis-trans isomerization, is more rapid in polar solvents than in nonpolar solvents. Linear solvation energy relationship (LSER) techniques show that this can be explained in terms of polarity and polarizability parameters for the solvent. Theoretical linear solvation energy relationship (TLSER) analysis shows that this can be explained in terms of solvent polarizability and electrostatic basicity. New TLSER descriptors based on calculated solvent bond diplole parameters are also successful in describing this solvent dependence. Solvent-dependent dipole moments are calculated for an approximate stilbene transition-state geometry using the polarizable continuum model (PCM), which suggests the usefulness of a more detailed study of this photoisomerization process using current solvation theory and computational techniques. © 1996 John Wiley & Sons, Inc. |
| Databáze: | OpenAIRE |
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