ROS Theses Repository

View Item 
  •   ROS Home
  • Engineering & Physical Sciences
  • Doctoral Theses (Engineering & Physical Sciences)
  • View Item
  •   ROS Home
  • Engineering & Physical Sciences
  • Doctoral Theses (Engineering & Physical Sciences)
  • View Item
  •   ROS Home
  • Engineering & Physical Sciences
  • Doctoral Theses (Engineering & Physical Sciences)
  • View Item
  • Admin
JavaScript is disabled for your browser. Some features of this site may not work without it.

Development and applications of quantum chemistry to open shell systems

View/Open
MurphyP_0617_eps.pdf (8.507Mb)
Date
2017-06
Author
Murphy, Paul
Metadata
Show full item record
Abstract
This thesis investigates the applicability of a range of computational techniques across a range of open shell chemical systems from the geometrically simple but electronically complex to the geometrically complex but electronically simple. Initially an investigation into a range of geometrically simple but electronically complicated systems is presented. The Monte Carlo Configuration Interaction method (MCCI) is applied to challenging transition metals dimers such as ScNi in order to establish the ground state potential energy surface, from equilibrium bond lengths through to dissociation using highly compact wavefunctions compared to Full Configuration Interaction (FCI). It shall be demonstrated that the ScNi dimer represents the current limit of this technique. Software development of MCCI is then undertaken in order to perform calculations of spin-orbit coupling interactions. Results on B, C, O, F, Si, S, F, Cl, OH, NO, CN and C2 species are shown to be comparable with other techniques using the one-electron Breit-Pauli Hamiltonian. The application of quantum chemistry to geometrically complex but electronically simple systems is then considered. Density Functional Theory (DFT) is used to investigate the mechanism and energetic barriers leading to ring inversion of the biscalix[4]arene supra-molecule. A minimum barrier height of 19.31 kcalmol−1 to inversion is elucidated along with details of the complete mechanistic pathway to inversion. The focus then moves to polymetallic clusters of calix[4]arene. A DFT study is made of the preferential binding of calix[4]arene towards first row transition metals of various oxidation and spin states. Results indicate that Cu3+ (singlet) species will preferentially bind to the lower rim over other metals in the study. The final DFT-related work presented is a study of the preferential binding at the upper rim of polymetallic calix[4]arene clusters towards a range of important small gas molecules. It was found that gases such as NH3 and SO2 bind most strongly to the upper rim with the inclusion of a transition metal at the lower rim providing strengthening of the host-guest binding.
URI
http://hdl.handle.net/10399/3355
Collections
  • Doctoral Theses (Engineering & Physical Sciences)

Browse

All of ROSCommunities & CollectionsBy Issue DateAuthorsTitlesThis CollectionBy Issue DateAuthorsTitles

ROS Administrator

LoginRegister
©Heriot-Watt University, Edinburgh, Scotland, UK EH14 4AS.

Maintained by the Library
Tel: +44 (0)131 451 3577
Library Email: libhelp@hw.ac.uk
ROS Email: open.access@hw.ac.uk

Scottish registered charity number: SC000278

  • About
  • Copyright
  • Accessibility
  • Policies
  • Privacy & Cookies
  • Feedback
AboutCopyright
AccessibilityPolicies
Privacy & Cookies
Feedback
 
©Heriot-Watt University, Edinburgh, Scotland, UK EH14 4AS.

Maintained by the Library
Tel: +44 (0)131 451 3577
Library Email: libhelp@hw.ac.uk
ROS Email: open.access@hw.ac.uk

Scottish registered charity number: SC000278

  • About
  • Copyright
  • Accessibility
  • Policies
  • Privacy & Cookies
  • Feedback
AboutCopyright
AccessibilityPolicies
Privacy & Cookies
Feedback