Calculation of fully non-adiabatic properties of the hydrogen molecular cation and its isotopomers

Valenzano, Loredana (2003) Calculation of fully non-adiabatic properties of the hydrogen molecular cation and its isotopomers. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

By using a scattering approach combined with a transformed Hamiltonian theory, fully non-adiabatic properties of the vibration-rotational levels of the ground electronic state of the hydrogen molecular cation H⁺₂ and its isotopomers, D⁺₂ and HD⁺, are studied. For low vibrational levels a variational method is also used, providing a check on the methods. The properties considered include the dissociation energies, the bond lengths and the dipole polarizabilities for all the three cations. Relativistic corrections are studied just for H⁺₂.

While properties such as bond lengths and dipole polarizabilities are studied through analytic integration, a numerical integration approach is developed to study the relativistic correlations, since singular integrands are involved. In addition, a new calculation method is developed so that the scattering method may be used.

Non-adiabatic dissociation energies and bond lengths are also studied for the tritium heteronuclear isotopomers HT⁺ and DT⁺.

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