DOI

10.17077/etd.e45d3ifx

Document Type

Dissertation

Date of Degree

Spring 2017

Access Restrictions

Access restricted until 07/03/2019

Degree Name

PhD (Doctor of Philosophy)

Degree In

Chemistry

First Advisor

Cheatum, Christopher M.

First Committee Member

Forbes, Tori Z.

Second Committee Member

Haes, Amanda J.

Third Committee Member

Mubeen, Syed

Fourth Committee Member

Quinn, Daniel M.

Abstract

Proton-transfer reactions are one of the most fundamental chemical reactions. However, the chemical dynamics of these processes remain elusive due to the difficulty of modeling these reactions. Establishing an experimental model system and using infrared absorption and two-dimensional infrared (2D IR) spectroscopies as means for detection, the chemical dynamics of the protonation states that are involved in a ground-electronic-state proton-transfer reaction in solution can be determined. In this study, experimental models are established with formic acid and nitrogenous bases in a low dielectric solvent. A hydrogen bond forms between the acid and the base, which will allow for the proton to transfer between the two molecules to form the neutral and the ion-pair protonation states. The carbon-deuterium (C-D) stretch and the carbonyl (C=O) stretch of the formic acid molecule are used as the reporter groups for the 2D IR measurements. The results of the C-D stretch demonstrate that there is a high sensitivity to the deprotonation, vibrational coupling, and vibrational dynamics trends that are linked to the solute-solvent interactions. The results of the C=O stretch demonstrate a sensitivity to the deprotonation and conformational disorder in which the position of the C=O changes the dynamics of the protonation state. Although, a proton-transfer is not detected, the experimental model system provides an understanding of the features that govern the chemical dynamics of proton-transfer reactions.

Keywords

Hydrogen Bonding, Infrared Spectroscopy, Proton Transfer, Two-dimensional infrared spectroscopy, Vibrational Dynamics, Vibrational Spectroscopy

Pages

xvii, 121 pages

Bibliography

Includes bibliographical references (pages 112-121).

Copyright

Copyright © 2017 Andrea Bray Grafton

Included in

Chemistry Commons

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