Application of the RPA and Higher RPA to the V and T States of Ethylene
- Creators
- Shibuya, Tai-Ichi
- McKoy, Vincent
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.
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.Attached Files
Published - SHIjcp71.pdf
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Additional details
- Eprint ID
- 33099
- Resolver ID
- CaltechAUTHORS:20120810-130411849
- Alfred P. Sloan Research Fellowship
- Created
-
2012-08-10Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Arthur Amos Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 4122