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Computational studies of heavy element complexes.

O'Grady, E.M.; (2005) Computational studies of heavy element complexes. Doctoral thesis , University of London. Green open access

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Abstract

This thesis reports the computational studies of the ground state electronic prop erties of AnOX5 n- (An=Pa, n=2 U, n=l Np, n=0 X=F, CI, Br), of C1M(PH3) 2 (M=Cu, Ag, Au, 111 ) and of MX3 (M-La-Lu, Ac-Lr X=H, F, CI, Br, I) us ing Density Functional Theory (DFT) and ab initio methods. Before presenting the results from these studies, the first chapter introduces computational studies of heavy element compounds through a discussion of selected studies taken from the literature. The second chapter introduces the electronic structure methods that were used during the course of this research. The results of this research are presented in chapters 3 to 5. Chapter 3 discusses DFT studies of the inverse trans influence (ITI) of AnOX5 n_ (An=Pa, n=2 U, n=l Np, n=0 X=F, CI, Br). These studies show that the ITI is due mainly to electronic factors at the equilibrium geometry, the 9ai molecular orbital of AnOXs n_, which is 7r* along the An-Xci5 bond, plays a key role in elongating the cis bond. In chapter 4, the metallophilic interactions of the 6d transactinide coinage metal, 111 , are presented. Comparison of the interaction energies of C1M(PH3) 2 (M=Cu, Ag, Au, 111 ), shows that with the exception of MP2, the post-HF (QCISD, CCSD and CCSD(T)) methods calculate that the interaction energies for the four complexes are approximately constant. The final results chapter (chapter 5) examines the influence of the 4f orbitals in determining the extent of pyramidality of LnX3 (Ln=La-Lu X=H, F-I) using the B3PW91 method. This study reports that the 4f orbitals reduce the extent of pyramidality via a reduction in the 5d orbital-based second-order Jahn-Teller distortion. A comparison between LnX3 and AnX3 (An=Ac-Lr X=H, F-I) is also made. The final chapter summarises the research.

Type: Thesis (Doctoral)
Title: Computational studies of heavy element complexes.
Identifier: PQ ETD:593078
Open access status: An open access version is available from UCL Discovery
Language: English
Additional information: Thesis digitised by Proquest
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: http://discovery.ucl.ac.uk/id/eprint/1445754
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