Title:
Theoretical Investigations of Pi-Pi and Sulfur-Pi Interactions and their Roles in Biomolecular Systems
Theoretical Investigations of Pi-Pi and Sulfur-Pi Interactions and their Roles in Biomolecular Systems
| dc.contributor.advisor | Sherrill, C. David | |
| dc.contributor.author | Tauer, Anthony Philip | en_US |
| dc.contributor.committeeMember | Bredas, Jean-Luc | |
| dc.contributor.committeeMember | Hernandez, Rigoberto | |
| dc.contributor.department | Chemistry and Biochemistry | en_US |
| dc.date.accessioned | 2006-01-18T22:25:04Z | |
| dc.date.available | 2006-01-18T22:25:04Z | |
| dc.date.issued | 2005-11-28 | en_US |
| dc.description.abstract | The study of noncovalent interactions between aromatic rings and various functional groups is a very popular topic in current computational chemistry. The research presented in this thesis takes steps to bridge the gap between theoretical prototypes and real-world systems. The non-additive contributions to the interaction energy in stacked aromatic systems are measured by expanding the prototype benzene dimer into trimeric and tetrameric systems. We show that the three- and four-body interaction terms generally do not contribute significantly to the overall interaction energy, and that the two-body terms are essentially the same as in the isolated dimer. The sulfur-pi interaction is then studied by using the hydrogen sufide-benzene dimer as a prototype system for theoretical predictions. We obtain higly-accurate potential energy curves, as well as an interaction energy extrapolated to the complete basis set limit. Energy decomposition analysis using symmetry-adapted perturbation theory shows that the sulfur-pi interaction is primarily electrostatic in nature. These theoretical results are then compared to an analysis of real sulfur-pi contacts found by searching protein structures in the Brookhaven Protein DataBank. We find that the most frequently seen configuration does not correspond to the theoretically predicted equilibrium for sydrogen sulfide-benzene, but instead to a configuration that suggests an alkyl-pi interaction involving the carbon adjacent to the sulfur atom. We believe our findings indicate that environmental effects within proteins are altering the energetics of the sulfur-pi interaction so that other functional groups are preferred for interacting with the aromatic ring. | en_US |
| dc.description.degree | M.S. | en_US |
| dc.format.extent | 478407 bytes | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.uri | http://hdl.handle.net/1853/7573 | |
| dc.language.iso | en_US | |
| dc.publisher | Georgia Institute of Technology | en_US |
| dc.subject | Symmetry-adapted perturbation theory | en_US |
| dc.subject.lcsh | Perturbation (Quantum dynamics) | en_US |
| dc.subject.lcsh | Molecular dynamics | en_US |
| dc.subject.lcsh | Molecular association | en_US |
| dc.subject.lcsh | Electronic structure | en_US |
| dc.subject.lcsh | Biomolecules | en_US |
| dc.title | Theoretical Investigations of Pi-Pi and Sulfur-Pi Interactions and their Roles in Biomolecular Systems | en_US |
| dc.type | Text | |
| dc.type.genre | Thesis | |
| dspace.entity.type | Publication | |
| local.contributor.advisor | Sherrill, C. David | |
| local.contributor.corporatename | School of Chemistry and Biochemistry | |
| local.contributor.corporatename | College of Sciences | |
| relation.isAdvisorOfPublication | 771cfa30-1ff7-4a12-b4c7-4f8e93b4860a | |
| relation.isOrgUnitOfPublication | f1725b93-3ab8-4c47-a4c3-3596c03d6f1e | |
| relation.isOrgUnitOfPublication | 85042be6-2d68-4e07-b384-e1f908fae48a |
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