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postgraduate thesis: Ab initio relativisticconsistent calculations and charge density and experimental massspectroscopic analysis of mono and polynuclearclusters of group 11 and 12 transition metals and metal chlorides: ySeyedabdolreza Sadjadi.
Title  Ab initio relativisticconsistent calculations and charge density and experimental massspectroscopic analysis of mono and polynuclearclusters of group 11 and 12 transition metals and metal chlorides: ySeyedabdolreza Sadjadi. 

Authors  
Issue Date  2013 
Publisher  The University of Hong Kong (Pokfulam, Hong Kong) 
Citation  Sadjadi, S.. (2013). Ab initio relativisticconsistent calculations and charge density and experimental massspectroscopic analysis of mono and polynuclear clusters of group 11 and 12 transition metals and metal chlorides / y Seyedabdolreza Sadjadi. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. Retrieved from http://dx.doi.org/10.5353/th_b5060577 
Abstract  The electron density function of molecular systems supplies a package of information. Quantum mechanical methods of producing and analyzing this function have been significantly improved during the past few years. The advent of accurate pseudopotentials and corresponding basis sets for KohnSham density functional and for postHartreeFock electroncorrelated approaches have enabled the inclusion of scalar relativistic and spinorbit coupling effects as well as electron correlation effects into the electron density function. The unpacking of the information embedded in such a function via the quantum theory of atoms in molecules (QTAIM) became possible by utilizing the very new subshell fitting method of reconstructing the density distribution of core electrons that had been replaced by the pseudopotentials.
These theoretical advances were applied in this thesis to characterize and explore the topological features of metalmetal bonding as one of the fundamental types of bonds formed between two elements. Group 11 and 12 transition metals which include gold and mercury as the most relativistic elements were the main focus of this work. Mono and polynuclear compounds (with up to 4 metal atoms) in both pure metal clusters and chlorocomplexes were studied by ab initio MØllerPlesset perturbation calculations followed by QTAIM analysis on the relaxed density. Some of these chlorocomplexes of copper, gold, zinc and cadmium metals were identified in the gas phase by mass spectrometric experiments. The general formulas of the set of molecules studied in group 11 were : M2, MCl, MCl+, MCl2, MCl2+, M2Cl+, M2Cl2^(s+), M2Cl3+, M3Cl2+, M3Cl3+, M3Cl5+, M4Cl5+ and M4Cl7+ and in group 12 were : M2, MCl, MCl+, MCl2, M2Cl3+, M3Cl5+, M4Cl7+ and M2^(s+). The topological features of metalmetal bonding were calculated along with atomic properties for each individual local minimum isomer found. The comparison of
the metalmetal bonding within the complexes and with the dimers revealed new
features of metalmetal bonding in 3d, 4d and 5d transition metal elements of
groups 11 and 12. With the aid of strong correlation between bond dissociation
energy and electron density at the location of the bond critical points found in the
case of dimers, the strength of the metalmetal bonding in the complexes was
estimated. The electron density’s basin properties calculated accurately for all the
clusters and their isomers in this thesis provided more insight also into the nature
of MCl bondings in the group 11 and 12 chloride clusters. Ultimately the bonding
information was used to predict the viability of these clusters in the gas phase. 
Degree  Doctor of Philosophy 
Subject  Metalmetal bonds. Transition metals. Chlorides. 
Dept/Program  Chemistry 
Persistent Identifier  http://hdl.handle.net/10722/188750 
DC Field  Value  Language 

dc.contributor.author  Sadjadi, Seyedabdolreza.   
dc.date.accessioned  20130908T15:07:56Z   
dc.date.available  20130908T15:07:56Z   
dc.date.issued  2013   
dc.identifier.citation  Sadjadi, S.. (2013). Ab initio relativisticconsistent calculations and charge density and experimental massspectroscopic analysis of mono and polynuclear clusters of group 11 and 12 transition metals and metal chlorides / y Seyedabdolreza Sadjadi. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. Retrieved from http://dx.doi.org/10.5353/th_b5060577   
dc.identifier.uri  http://hdl.handle.net/10722/188750   
dc.description.abstract  The electron density function of molecular systems supplies a package of information. Quantum mechanical methods of producing and analyzing this function have been significantly improved during the past few years. The advent of accurate pseudopotentials and corresponding basis sets for KohnSham density functional and for postHartreeFock electroncorrelated approaches have enabled the inclusion of scalar relativistic and spinorbit coupling effects as well as electron correlation effects into the electron density function. The unpacking of the information embedded in such a function via the quantum theory of atoms in molecules (QTAIM) became possible by utilizing the very new subshell fitting method of reconstructing the density distribution of core electrons that had been replaced by the pseudopotentials. These theoretical advances were applied in this thesis to characterize and explore the topological features of metalmetal bonding as one of the fundamental types of bonds formed between two elements. Group 11 and 12 transition metals which include gold and mercury as the most relativistic elements were the main focus of this work. Mono and polynuclear compounds (with up to 4 metal atoms) in both pure metal clusters and chlorocomplexes were studied by ab initio MØllerPlesset perturbation calculations followed by QTAIM analysis on the relaxed density. Some of these chlorocomplexes of copper, gold, zinc and cadmium metals were identified in the gas phase by mass spectrometric experiments. The general formulas of the set of molecules studied in group 11 were : M2, MCl, MCl+, MCl2, MCl2+, M2Cl+, M2Cl2^(s+), M2Cl3+, M3Cl2+, M3Cl3+, M3Cl5+, M4Cl5+ and M4Cl7+ and in group 12 were : M2, MCl, MCl+, MCl2, M2Cl3+, M3Cl5+, M4Cl7+ and M2^(s+). The topological features of metalmetal bonding were calculated along with atomic properties for each individual local minimum isomer found. The comparison of the metalmetal bonding within the complexes and with the dimers revealed new features of metalmetal bonding in 3d, 4d and 5d transition metal elements of groups 11 and 12. With the aid of strong correlation between bond dissociation energy and electron density at the location of the bond critical points found in the case of dimers, the strength of the metalmetal bonding in the complexes was estimated. The electron density’s basin properties calculated accurately for all the clusters and their isomers in this thesis provided more insight also into the nature of MCl bondings in the group 11 and 12 chloride clusters. Ultimately the bonding information was used to predict the viability of these clusters in the gas phase.   
dc.language  eng   
dc.publisher  The University of Hong Kong (Pokfulam, Hong Kong)   
dc.relation.ispartof  HKU Theses Online (HKUTO)   
dc.rights  The author retains all proprietary rights, (such as patent rights) and the right to use in future works.   
dc.rights  Creative Commons: Attribution 3.0 Hong Kong License   
dc.source.uri  http://hub.hku.hk/bib/B5060577X   
dc.subject.lcsh  Metalmetal bonds.   
dc.subject.lcsh  Transition metals.   
dc.subject.lcsh  Chlorides.   
dc.title  Ab initio relativisticconsistent calculations and charge density and experimental massspectroscopic analysis of mono and polynuclearclusters of group 11 and 12 transition metals and metal chlorides: ySeyedabdolreza Sadjadi.   
dc.type  PG_Thesis   
dc.identifier.hkul  b5060577   
dc.description.thesisname  Doctor of Philosophy   
dc.description.thesislevel  Doctoral   
dc.description.thesisdiscipline  Chemistry   
dc.description.nature  published_or_final_version   
dc.identifier.doi  10.5353/th_b5060577   
dc.date.hkucongregation  2013   