Structural determination of hydrogen-bonded clusters nucleated by large aromatic hydrocarbons and 7-aminocoumarins.

Format:

Book

Thesis/Dissertation

Author/Creator:

Palmer, Phillip Mark.

Contributor:

Topp, Michael R., advisor.

University of Pennsylvania.

Language:

English

Subjects (All):

Molecular theory.

Molecules.

Chemistry, Physical and theoretical.

0494.

0609.

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Local Subjects:

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

0494.

0609.

Physical Description:

370 pages

Contained In:

Dissertation Abstracts International 61-10B.

System Details:

Mode of access: World Wide Web.

text file

Summary:

IR-UV double resonance spectroscopy of hydrogen-bonded clusters of water and methanol nucleated by the aromatic hydrocarbons perylene and anthracene, as well as a series of 7-aminocoumarins are investigated. These clusters have been mass selected using near-threshold R2PI in a linear TOF-MS. Infrared spectra in the fundamental OH stretch region, 3000--3800 cm -1 coupled with DFT vibrational simulations permit structural assignment for many of the clusters investigated.

While methanol clusters on anthracene and perylene are similar to their benzene counterparts, the IR spectra of perylene-based water clusters display a new type of hydrogen bonding not found in other systems. In one instance, perylene: (H2O)6, the IR spectrum suggests the presence of a structure different from the cage found for the pure and benzene systems. MRES of anthracene: (H2O)n, n = 1--16, suggest structures based on fused tetramer and penatmer rings are particularly stable in the jet expansion.

Studies on C151: (H2O)n, n = 1--5, C152A: (H2O)n, n = 1--3, and C153: (H2O) n, n = 1--2, indicate that not only is the site of hydrogen-bonding interaction dependent on the substitution pattern of the coumarin, but is also cluster-size dependent. Each of the coumarins showed two n = 1 conformers, each species demonstrating very different electronic properties, both in electronic excitation and ionization.

This thesis has been organized into four sections: Introduction, Experimental, Hydrocarbons, and 7-Aminocoumarins. While there is continuity between the chapters, each can be read separately without much loss of understanding or confusion. This being said, a brief glance through the Experimental will get one familiar with many of the acronyms used later in the thesis.

Notes:

Thesis (Ph.D. in Chemistry) -- University of Pennsylvania, 2000.

Source: Dissertation Abstracts International, Volume: 61-10, Section: B, page: 5344.

Supervisor: Michael R. Topp.

Local Notes:

School code: 0175.

ISBN:

9780599970601

Access Restriction:

Restricted for use by site license.