| dc.contributor.author | Viswanathan, Balakrishnan. | en_US |
| dc.date.accessioned | 2014-10-21T12:35:23Z | |
| dc.date.available | 2005 | |
| dc.date.issued | 2005 | en_US |
| dc.identifier.other | AAINR08426 | en_US |
| dc.identifier.uri | http://hdl.handle.net/10222/54758 | |
| dc.description | The Born-Oppenheimer approximation is one of the cornerstones upon which modern quantum chemistry is founded. The application of this approximation has it made it possible to perform the vast number of computations performed. However, it must be recalled that the BO method is an approximation. It is therefore preferable to have a method that performs well without the need for invoking the above approximation. | en_US |
| dc.description | This document outlines the development of a novel method for the ab initio computation of molecular systems wherein the Born-Oppenheimer approximation is not invoked. A brief overview of previous methods developed to solve this problem will be presented, mentioning reasons why these methods are inadequate. This will be followed by the development of the new method and its physical implications. Some recent results are also presented. | en_US |
| dc.description | The thermochemistry and geometries of cation and anion complexes with water, ammonia, formaldehyde, and formamide are essential to understand the solvation and desolvation processes occurring in biological systems. However, experimental data are only available for the interaction of Group I metal cations with water. The thermochemistry and geometries of metal cations with the other mentioned ligands are less well characterised. Theoretical methods afford an alternate method to understanding these systems. | en_US |
| dc.description | This study was designed to generate an optimal B3LYP-based computational scheme for the calculation of metal cation-ligand clusters. The cation cluster geometries converge only at the 6-311+G(3df,3pd) level. Basis set superposition errors (BSSE) are found to vary from ∼0.2 to ∼5 kcal mol-1 , and are significant for all basis sets smaller than 6-311+G(3df,3pd). Geometry convergence and BSSE disappearance occur only at the 6-311+G(3df,3pd) level, and hence this is the ideal method to employ. Unfortunately, it was also discovered that currently available methods are unable to adequately describe the anion-water clusters, mainly due to the residual BSSE even when the largest basis sets are used. | en_US |
| dc.description | Thesis (Ph.D.)--Dalhousie University (Canada), 2005. | en_US |
| dc.language | eng | en_US |
| dc.publisher | Dalhousie University | en_US |
| dc.publisher | | en_US |
| dc.subject | Chemistry, Analytical. | en_US |
| dc.title | The development of a non-Born-Oppenheimer self-consistent field method and computational cluster studies on the solvation of cations and anions. | en_US |
| dc.type | text | en_US |
| dc.contributor.degree | Ph.D. | en_US |
