Hyperpolarizabilities of Push—Pull Polyenes Molecular Orbital and Valence-Bond Charge-Transfer Models
Abstract
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.
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).Additional details
- Eprint ID
- 85672
- Resolver ID
- CaltechAUTHORS:20180406-080326593
- Air Force Office of Scientific Research (AFOSR)
- NASA
- NSF
- North Atlantic Treaty Organization (NATO)
- Fonds de la Recherche Scientifique (FNRS)
- Belgian Federal Science Policy Office (BELSPO)
- Created
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2018-04-06Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field
- Series Name
- ACS Symposium Series
- Series Volume or Issue Number
- 601
- Other Numbering System Name
- WAG
- Other Numbering System Identifier
- 0317