The framework of density functional theory is used to define rigorously quantities of general chemical interest and investigate their properties. The computational schemes for calculating their values are based on the topological theory of atoms in molecules. General and spin-specific atomic Fukui indices are defined and calculated for six model molecular systems. The ROHF level of theory is estimated as the least expensive method for their evaluation which produces reliable results. A scheme for energy decomposition of molecular interactions, which is applicable to any level of electronic structure theory, is proposed. The scheme partitions the interaction energy into classical electrostatic, charge-transfer, and wave function relaxation components, which are true observables converging smoothly with increasing basis sets. Results of several test calculations are compared with those produced by other energy partitioning schemes and found to exhibit superior numerical stability. The atomic softness matrix, which is a generalization of the Huckel atom-atom polarizability matrix, is defined and used in a rigorous reformulation of the electronegativity equalization methods. A computational scheme for its evaluation is proposed and illustrated with several numerical examples. The charge distribution in substituted polyynes is investigated with the new formalism. Individual spin contributions to charge transfer in molecules are analysed. The intra- and interspin components of the bond hardness tensor are rigorously defined. Stability conditions with respect to charge transfer and spin polarization are formulated for closed-shell systems. The energetics of electron flow is illustrated using model systems. Some non-specific electrostatic effects of solvation in polar molecular systems are studied using a simple continuum-type model. The analysis of these effects / in terms of electronegativity equalization and charge transfer show that, based on the electrostatics of their solvation, most systems fall into two categories according to the solvation induced molecular geometry change. / Source: Dissertation Abstracts International, Volume: 56-06, Section: B, page: 3216. / Major Professor: Jerzy Cioslowski. / Thesis (Ph.D.)--The Florida State University, 1995.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_77472 |
| Contributors | Martinov, Martin Nikolov., Florida State University |
| Source Sets | Florida State University |
| Language | English |
| Detected Language | English |
| Type | Text |
| Format | 110 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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