A Caltech Library Service

Hyperpolarizabilities of Push—Pull Polyenes Molecular Orbital and Valence-Bond Charge-Transfer Models

Perry, J. W. and Marder, S. R. and Meyers, F. and Lu, D. and Chen, G. and Goddard, W. A., III and Brédas, J. L. and Pierce, B. M. (1995) Hyperpolarizabilities of Push—Pull Polyenes Molecular Orbital and Valence-Bond Charge-Transfer Models. In: Polymers for Second-Order Nonlinear Optics. ACS Symposium Series. No.601. American Chemical Society , Washington, DC, pp. 45-56. ISBN 9780841232631.

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item:


In this paper we review two theoretical approaches that illustrate the relationships between molecular (hyper)polarizabilities and bondlength alternation (BLA). In one approach, we employ sum-overstates calculations at the INDO-SDCI level on (CH_3)_2N-(CH=CH)_4-CHO, including an external, static, homogeneous electric field that unes the degree of ground-state polarization and BLA. In the second approach, we use a simple semiclassical model, wherein the mixing of valence bond (VB) and charge-transfer (CT) states along a BLA coordinate is treated. Qualitatively, the two approaches give very similar structure-property trends, that are consistent with experimental hyperpolarizability data on donor-acceptor polyenes. The agreement of the calculated trends reflects the importance of VB-CT energetics in determining them.

Item Type:Book Section
Related URLs:
URLURL TypeDescription
Goddard, W. A., III0000-0003-0097-5716
Additional Information:© 1995 American Chemical Society. Received April 19, 1995. Published in print 11 August 1995. The research described in this paper was performed in part by the Jet Propulsion Laboratory, (JPL) California Institute of Technology, as part of its Center for Space Microelectronics Technology and was supported by the Advanced Research Projects Agency (administered by the Air Force Office of Scientific Research) and the Ballistic Missiles Defense Initiative Organization, Innovative Science and Technology Office, through a contract with the National Aeronautics and Space Administration (NASA). Support at the Beckman Institute from the National Science Foundation, the Air Force Office of Scientific Research and the North Atlantic Treaty Organization is gratefully acknowledged. The work in Mons was carried out within the framework of the Belgium Prime Minister's Office of Science Policy "Pôle d'Attraction Interuniversitaire en Chimie Supramoléculaire et Catalyse" and "Programme d'Implulsion en Technologie de l'lnformation" and is partly supported by the Belgium National Fund for Scientific Research (FNRS).
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
North Atlantic Treaty Organization (NATO)UNSPECIFIED
Fonds de la Recherche Scientifique (FNRS)UNSPECIFIED
Belgian Federal Science Policy Office (BELSPO)UNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Series Name:ACS Symposium Series
Issue or Number:601
Record Number:CaltechAUTHORS:20180406-080326593
Persistent URL:
Official Citation:Hyperpolarizabilities of Push—Pull Polyenes J. W. Perry, S. R. Marder, F. Meyers, D. Lu, G. Chen, W. A. Goddard, III, J. L. Brédas, and B. M. Pierce Polymers for Second-Order Nonlinear Optics. August 11, 1995, 45-56 DOI:10.1021/bk-1995-0601.ch003
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85672
Deposited By: Ruth Sustaita
Deposited On:06 Apr 2018 16:06
Last Modified:15 Nov 2021 20:31

Repository Staff Only: item control page