Link to the University of Pittsburgh Homepage
Link to the University Library System Homepage Link to the Contact Us Form

Charge transfer by electronic excitation: High resolution measurements via rotationally resolved spectroscopy in the gas phase

Fleisher, Adam Joseph (2011) Charge transfer by electronic excitation: High resolution measurements via rotationally resolved spectroscopy in the gas phase. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

Primary Text

Download (5MB) | Preview


Understanding the intricate molecular motions that occur in solvents is a scientific challenge for many fields, including biology, chemistry, and physics. Solvents are ever-present in living organisms, and may play a vital role in the folding of proteins and nucleic acid chains. Currently, ultrafast spectroscopic techniques are able to map long range networks of hydrogen bonds within the universal solvent water, where hindered motions are important. Presented in this dissertation is a detailed study of several highly resolved frequency spectra, each of which makes a unique contribution to the understanding of molecular structure, intermolecular bonding dynamics, and the forces that stabilize hydrogen bonds in the gas phase. It is here, in an isolated environment, that solute-solvent interactions can be dissected, both experimentally and theoretically, void of perturbations from the bulk. Among the molecular systems investigated here, the photoacid β-naphthol was studied in the presence of water and ammonia, and the electric dipole moments of each complex were shown to contain intrinsic contributions from intermolecular charge transfer. This charge transfer is present in the ground electronic state, and increases upon excitation with ultraviolet light. Two rotamers of the donor-acceptor system meta-aminobenzoic acid have been identified by differences in their moments of inertia and dipole moments, and singly and doubly solvated complexes of this system were observed. The ground, S1, and S2 dipole moments of anomalous dual fluorescence molecules, such as DMABN and phenylpyrrole, have also been determined, and their relevance to condensed phase solvatochromism is discussed.The work reported here makes use of two ultraviolet laser spectrometers; a pulsed supersonic jet spectrometer, and a high resolution continuous wave molecular beam spectrometer. A wide variety of ab initio calculations were performed in support of these experiments.


Social Networking:
Share |


Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Fleisher, Adam
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairPratt, David W.pratt@pitt.eduPRATT
Committee MemberPlusquellic, David
Committee MemberWaldeck, David H.dave@pitt.eduDAVE
Committee MemberJordan, Kenneth D.ken@visual1.chem.pitt.eduJORDAN
Date: 25 September 2011
Date Type: Completion
Defense Date: 15 August 2011
Approval Date: 25 September 2011
Submission Date: 17 August 2011
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: amino acids; charge transfer; photoacids; proton transfer; solvatochromism; solvation; astronomy; line spectra; molecular spectroscopy; quantum mechanics; astrochemistry; chemical reactions; acid base reactions; excited states; hydrogen bonds
Other ID:, etd-08172011-000723
Date Deposited: 10 Nov 2011 20:00
Last Modified: 15 Nov 2016 13:49


Monthly Views for the past 3 years

Plum Analytics

Actions (login required)

View Item View Item