Properties and applications of the average interparticle distance
Thesis (Ph.D.)--Memorial University of Newfoundland, 2009. Chemistry Includes bibliographical references. The first and second moment operators are used to define the origin invariant shape and size of a molecule or functional group, as well as expressions for the distance between two electrons and...
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ftmemorialunivdc:oai:collections.mun.ca:theses4/71969 2023-05-15T17:23:33+02:00 Properties and applications of the average interparticle distance Hollett, Joshua W. Memorial University of Newfoundland. Dept. of Chemistry 2009 xiii, 178 leaves : ill. (some col.) Image/jpeg; Application/pdf http://collections.mun.ca/cdm/ref/collection/theses4/id/71969 Eng eng Electronic Theses and Dissertations (18.03 MB) -- http://collections.mun.ca/PDFs/theses/Hollett_JoshuaW.pdf a3244233 http://collections.mun.ca/cdm/ref/collection/theses4/id/71969 The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. Paper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries Electron-electron interactions Electronic structure Text Electronic thesis or dissertation 2009 ftmemorialunivdc 2015-08-06T19:22:11Z Thesis (Ph.D.)--Memorial University of Newfoundland, 2009. Chemistry Includes bibliographical references. The first and second moment operators are used to define the origin invariant shape and size of a molecule or functional group, as well as expressions for the distance between two electrons and the distance between an electron and a nucleus. The measure of molecular size correlates quite well with an existing theoretical measure of molecular volume calculated from isodensity contours. Also, the measure of size is effective in predicting steric effects of substituents which have been measured experimentally. The electron-electron and electron-nuclear distances are related to components of the Hartree-Fock energy. The average distance between two electrons models the Coulomb energy quite well, especially in the case of localized molecular orbitals. The average distance between an electron and a nucleus is closely related to the electron-nuclear attraction energy of a molecule. -- The relationships discovered between the average interparticle distances and molecular energy components have led to the development of a new empirical approach to modelling the electronic structure of molecules. The general energy expression for a simulated electronic structure theory is defined, along with the functional form of the interatomic distance dependent energy functions. The theory is used to model the hydrogen molecule, the first-row hydrides, and ethane. The models, which have the correct RHF/6-3lG(d) optimized geometries, also fit the RHF/6-31G(d) energy at equilibrium and the UHF/6-31G(d) energy at the bond dissociation limit, as well as some vibrational frequencies. -- Also directly related to the interelectronic distance, is the issue of electron correlation. Several new approaches to the electron correlation problem have emerged in recent years. Among the new methods is orbital functional theory, in which the correlation energy is a functional of the molecular orbitals. The correlation energy of different isoelectronic series as a function of nuclear charge is investigated in an effort to design a correlation operator. Insight is also gained by examining the explicit CISD energy expression. Thesis Newfoundland studies University of Newfoundland Memorial University of Newfoundland: Digital Archives Initiative (DAI) Hartree ENVELOPE(-44.716,-44.716,-60.783,-60.783) |
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Memorial University of Newfoundland: Digital Archives Initiative (DAI) |
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ftmemorialunivdc |
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English |
topic |
Electron-electron interactions Electronic structure |
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Electron-electron interactions Electronic structure Hollett, Joshua W. Properties and applications of the average interparticle distance |
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Electron-electron interactions Electronic structure |
description |
Thesis (Ph.D.)--Memorial University of Newfoundland, 2009. Chemistry Includes bibliographical references. The first and second moment operators are used to define the origin invariant shape and size of a molecule or functional group, as well as expressions for the distance between two electrons and the distance between an electron and a nucleus. The measure of molecular size correlates quite well with an existing theoretical measure of molecular volume calculated from isodensity contours. Also, the measure of size is effective in predicting steric effects of substituents which have been measured experimentally. The electron-electron and electron-nuclear distances are related to components of the Hartree-Fock energy. The average distance between two electrons models the Coulomb energy quite well, especially in the case of localized molecular orbitals. The average distance between an electron and a nucleus is closely related to the electron-nuclear attraction energy of a molecule. -- The relationships discovered between the average interparticle distances and molecular energy components have led to the development of a new empirical approach to modelling the electronic structure of molecules. The general energy expression for a simulated electronic structure theory is defined, along with the functional form of the interatomic distance dependent energy functions. The theory is used to model the hydrogen molecule, the first-row hydrides, and ethane. The models, which have the correct RHF/6-3lG(d) optimized geometries, also fit the RHF/6-31G(d) energy at equilibrium and the UHF/6-31G(d) energy at the bond dissociation limit, as well as some vibrational frequencies. -- Also directly related to the interelectronic distance, is the issue of electron correlation. Several new approaches to the electron correlation problem have emerged in recent years. Among the new methods is orbital functional theory, in which the correlation energy is a functional of the molecular orbitals. The correlation energy of different isoelectronic series as a function of nuclear charge is investigated in an effort to design a correlation operator. Insight is also gained by examining the explicit CISD energy expression. |
author2 |
Memorial University of Newfoundland. Dept. of Chemistry |
format |
Thesis |
author |
Hollett, Joshua W. |
author_facet |
Hollett, Joshua W. |
author_sort |
Hollett, Joshua W. |
title |
Properties and applications of the average interparticle distance |
title_short |
Properties and applications of the average interparticle distance |
title_full |
Properties and applications of the average interparticle distance |
title_fullStr |
Properties and applications of the average interparticle distance |
title_full_unstemmed |
Properties and applications of the average interparticle distance |
title_sort |
properties and applications of the average interparticle distance |
publishDate |
2009 |
url |
http://collections.mun.ca/cdm/ref/collection/theses4/id/71969 |
long_lat |
ENVELOPE(-44.716,-44.716,-60.783,-60.783) |
geographic |
Hartree |
geographic_facet |
Hartree |
genre |
Newfoundland studies University of Newfoundland |
genre_facet |
Newfoundland studies University of Newfoundland |
op_source |
Paper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries |
op_relation |
Electronic Theses and Dissertations (18.03 MB) -- http://collections.mun.ca/PDFs/theses/Hollett_JoshuaW.pdf a3244233 http://collections.mun.ca/cdm/ref/collection/theses4/id/71969 |
op_rights |
The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. |
_version_ |
1766113264626827264 |