Title

Terahertz spectroscopy and molecular modeling of molecules connected by a network of non-covalent interactions

Date of Award

2009

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Advisor(s)

Timothy M. Korter

Keywords

Terahertz, Molecular modeling, Hydrogen-bonding, Electrostatic interactions, Cluster formation

Subject Categories

Chemistry | Physical Chemistry | Physical Sciences and Mathematics

Abstract

Experimental terahertz (THz) spectroscopy and molecular modeling were used to investigate the network of non-covalent interactions that serve to connect molecules in the solution-phase and solid-state. The intermolecular forces found in the molecules studied included hydrogen-bonding, electrostatic interactions, π-π stacking, and long-range dispersion forces. These types of non-covalent forces define cluster formation in solution and the packing arrangement of a crystalline solid. Molecular modeling was utilized to predict the structure and vibrations of the samples and guide the analysis of the experimental data. For solution-phase experiments, isolated-molecule calculations were carried out using density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) methods. Solid-state DFT using periodic boundary conditions was used to interpret crystalline solids. These periodic calculations include the relevant molecular environment found in solids which isolated-molecule calculations can not provide. In all cases, several density functionals were tested to determine how well they reproduce the experimental observation of structure and THz motions.

Access

Surface provides description only. Full text is available to ProQuest subscribers. Ask your Librarian for assistance.

http://libezproxy.syr.edu/login?url=http://proquest.umi.com/pqdweb?did=1913184221&sid=1&Fmt=2&clientId=3739&RQT=309&VName=PQD

Link to Full Text

Share

COinS