Date of Completion
alkali clusters, van der waals, field control, thermochemistry, quantum chemistry
John Montgomery Jr
H. Harvey Michels
Field of Study
Doctor of Philosophy
The calculation of non-covalent interactions of highly polarizable molecules is an outstanding problem in chemistry and physics. Difficulties arise both in accurate treatments of dispersion interactions between molecules and in the evaluation of surfaces of sufficient size for use in further computations. While ``gold-standard" calculations using coupled cluster theory with singles, doubles and perturbative triples provides a reliable method for evaluating interactions the computational cost involved in calculating more than a few points of an interaction surface becomes prohibitive for even medium sized molecules. Expanding the long range interaction into a van der Waals series reduces the cost of evaluating a surface to the computation of a few parameters. We describe here the implementation of a new computer program for calculating van der Waals coefficients for arbitrary molecules using the sum over states method. The laboratory-frame transformation of the computed van der Waals surface and the inclusion of rotational state dressing on the surface is derived. Analytic approximations for the interactions of two linear molecules in the presence of a small DC electric field are also derived. Recent achievements in the formation and manipulation of ultracold polar molecules have opened the door to exciting new studies in cold chemical reactions. To characterize the energetics and reaction pathways of trimer and tetramer formation and reactions, we have computed the structure and thermochemistry of the model trimer Li$_3$ and every X$_2$Y$_2$ alkali tetramer through Cs. Related interest in the control of molecular ion reactions is also investigated with recent theoretical results for the rubidium hydroxide reaction presented here.
Byrd, Jason N., "Ultracold Chemistry of Alkali Clusters" (2013). Doctoral Dissertations. 53.