Date of Completion

4-8-2013

Embargo Period

4-8-2013

Keywords

Ab initio, Molecular ions, Gold nanoclusters, QM/MM, DFT, Electronic structure, Potential energy curves, Hyperfine structure, Non-adiabatic corrections

Major Advisor

Dr. Robin Cote

Associate Advisor

Dr. John Montgomery, Jr.

Associate Advisor

Dr. Jose Gascon

Field of Study

Physics

Degree

Doctor of Philosophy

Open Access

Open Access

Abstract

Alkaline-earth dimers are now been used, as new grounds for, testing fundamental physics laws, precision measurements and quantum computation. As a starting point for such experiments, one needs a very good knowledge of the electronic structure, energetics and long-range behavior of these molecular ions. We perform accurate ab initio calculations for the ground and low-lying excited states of Be2+, Mg2+, Ca2+ and Sr2+ molecular ions. We have also calculated the spectroscopic constants, electronic transition dipole moments, polarizabilities and long-range dispersion coefficients for the various alkaline-earth ionic dimers. We have extended our calculations to study heteronuclear species of alkaline-earth molecular ions, like BeCa+, and also mixed alkali alkaline-earth species like NaCa+. We calculated photoassociation (PA) pathways for formation of cold molecular ions and also studied corrections to the Born-Oppenheimer Hamiltonian: non-adiabatic couplings and hyperfine structure due to nuclear spins and electric quadrupoles. We believe, this work would lay foundation, not only for new experiments in ultracold physics and chemistry, but would also provide valuable starting point for theoretical calculations involving low temperature scattering and resonant charge transfer.

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