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Application of the RPA and Higher RPA to the V and T States of Ethylene

Shibuya, Tai-Ichi and McKoy, Vincent (1971) Application of the RPA and Higher RPA to the V and T States of Ethylene. Journal of Chemical Physics, 54 (4). pp. 1738-1751. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120810-130411849

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Abstract

We have applied our proposed higher random‐phase approximation (HRPA) to the T and V states of ethylene. In the HRPA, unlike the RPA, one solves for the excitation frequencies and the ground‐state correlations self‐consistently. We also develop a simplified scheme (SHRPA) for solving the equations of the HRPA, using only molecular integrals sufficient for the usual RPA calculations. The HRPA removes the triplet instability which often occurs in the RPA. The excitation energy for the N → T transition is now in good agreement with experiment. The N → V transition energy increases by 15% over its RPA Value. The N → V oscillator strength changes only very slightly. These results are also useful in explaining the appearance and ordering of states obtained in recent direct open‐shell SCF calculations.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1675081DOIUNSPECIFIED
http://jcp.aip.org/resource/1/jcpsa6/v54/i4/p1738_s1PublisherUNSPECIFIED
Additional Information:© 1971 American Institute of Physics. Received 24 August 1970. We thank Dr. Thomas Dunning for carrying out the calculations discussed in Sec. VII and providing many results and computer programs needed in the TDA and RPA calculations. One of us (T.S.) would like to thank Dr. Carl Wulfman of the University of the Pacific for helpful discussions. Alfred P. Sloan Foundation Fellow. Contribution No. 4122.
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Funding AgencyGrant Number
Alfred P. Sloan Research FellowshipUNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics4122
Record Number:CaltechAUTHORS:20120810-130411849
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120810-130411849
Official Citation: Application of the RPA and Higher RPA to the V and T States of Ethylene Tai‐Ichi Shibuya and Vincent McKoy J. Chem. Phys. 54, 1738 (1971); http://dx.doi.org/10.1063/1.1675081
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33099
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:10 Aug 2012 20:22
Last Modified:26 Dec 2012 15:57

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