Campus Access Only

All rights reserved. This publication is intended for use solely by faculty, students, and staff of University of the Pacific. No part of this publication may be reproduced, distributed, or transmitted in any form or by any means, now known or later developed, including but not limited to photocopying, recording, or other electronic or mechanical methods, without the prior written permission of the author or the publisher.

Date of Award


Document Type

Thesis - Pacific Access Restricted

Degree Name

Master of Science (M.S.)



First Advisor

Carl E. Wulfman

First Committee Member

Alex Granik

Second Committee Member

Larry O. Spreer

Third Committee Member

Bruce W. Shore

Fourth Committee Member

Richard L. Perry


Quantum mechanical calculations were used to examine the polarization of excited singlet states of twisted conjugated systems. This study began as an investigation of systems which are symmetric about a central double bond. Symmetry requires that when twisting about such a bold, there must be a crossing of two low-lying states. At the one election level of theory, this leads to a degeneracy between the ground state and first excited state at 90°of twist. Slight perturbations to the twisted system will mix the two degenerate states and lead to a highly polar condition. This was confirmed on the one-electron level with calculations on several symmetrically twisted conjugated systems.

Further calculations indicated that there were crossings between two low-lying states for twisting about certain non-central double bonds as well. It was hypothesized from the results of simple calculations, that the pairing theorem of alternant hydrocarbons provides a framework that explains where and why these non-symmetry determined crossings occur. In general, the implications of the pairing theorem are that twisting a neutral even-alternant hydrocarbon about any double bond should lead to a crossing of two low-lying states.

Upon further i:tivestigation of the connection between the pairing theorem and twisted excited states, the theorem's predictions were confirmed by MNDO calculations. Furthermore, it was shown that small perturbations applied to these systems when the two states become nearly degenerate led to a dramatic polarization across the twisted double bond.

It was found that there are also highly polarizable twisted excited states whose existence is not predicted by the pairing theorem.



To access this thesis/dissertation you must have a valid email address and log-in to Scholarly Commons.

Find in PacificSearch



If you are the author and would like to grant permission to make your work openly accessible, please email


Rights Statement

Rights Statement

In Copyright. URI:
This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).