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Please use this identifier to cite or link to this item: http://hdl.handle.net/1959.13/38359
- Ab Initio investigation of the electronic structure and rovibrational spectroscopy of group-I and II metal hydrides and helides
Page, Alister J.
- University of Newcastle. Faculty of Science and Information Technology, School of Environmental and Life Sciences
- Research Doctorate - Doctor of Philosophy (PhD)
- (**Note: this abstract is a plain text version of the author's abstract, the original of which contains characters and symbols which cannot be accurately represented in this format. The properly formatted abstract can be viewed in the Abstract and Thesis files above.**) The electronic structure and rovibrational spectroscopy of MH2, MHn+2, HMHen+ and MHen+2 (M = Li, Be, Na, Mg, K, Ca; n = 1, 2) have been investigated using correlated ab initio ansatz. In order to determine the efficacy of various electronic structure methods with respect to Group-I and II hydrides and helides, atomic properties of Li, Be,Na, Mg, K and Ca were calculated. Relativistically-corrected UCCSD(T) and ICMRCI(+Q) were deemed to be the most suitable ansatz with respect to both efficiency and accuracy. The lowest 2A1 and 2Σ- states of MH2 were found to be purely repulsive, in agreement with previous predictions. The main factor determining the structure and stability of the excited states of MH2 was the relative orientations and occupations of the valence p atomic orbital of M and the H2 1Ou orbital. The ground states of MHn+2 were found to be the result of the charge-quadrupole interaction between Mn+ and the H2 molecular subunit. The structures of the ground states of HMHe+ were extremely uxional with respect to the central bond angle co-ordinate. The ground state PESs of MHe+2 were also extremely sensitive to the ab initio ansatz by which they are modelled. The respective bonding of the H and He in both HMHe+ and HMHe2+ appeared to be charge-dependent in the case of Be, Mg and Ca. Despite the weak bonding observed for the Group-II hydrohelide and helide monocations, the corresponding dications each exhibit thermodynamically stable equilibria. The solution algorithm of von Nagy-Felsobuki and co-workers was employed in the calculation of vibrational and rovibrational spectra. This algorithm employed an Eckart-Watson Hamiltonian in conjunction with rectilinear normal co-ordinates. Vibrational and rovibrational Hamiltonian matrices were diagonalised using variational methods. This algorithm was extended so that the vibration transition moment integrals, and hence vibrational radiative properties, of linear triatomic molecules could be calculated. A method by which vibration-averaged structures are calculated was also developed and implemented. Analytical potential energy functions (PEFs) and dipole moment functions (DMFs) of (1A1)LiH+2, (1A1)NaH+2, (1A1)BeH2+2,(1A1)MgH2+2, (1Σ+g )BeHe2+2, (2Σ+)HBeHe2+, (1Σ+g )MgHe2+2 and (2Σ+)HMgHe2+ were developed using leastsquare regression techniques in conjunction with discrete ab initio grids. Vibrational structures and spectra of these species were subsequently calculated. In addition, the rovibrational spectra of (1A1)LiH+2, (1A1)NaH+2, (1A1)BeH2+2 and (1A1)MgH2+2 were calculated. For (1A1)LiH+2 and (1A1)LiD+2 , calculated rovibrational transition frequencies for J ≤ 10 and 0 ≤ K ≤ 3 were within ca. 0.1-0.2% of experimental values.
- University of Newcastle Research Higher Degree Thesis
molecular hydride cation;
molecular helide cation;
- Resource Type
- Copyright 2008 Alister J. Page
- Full Text