Bender, Charles F. and Dunning, Thom. H., Jr. and Schaefer, Henry F., III and Goddard, William A., III and Hunt, William J. (1972) Multiconfiguration wavefuntions for the lowest (ππ*) excited states of ethylene. Chemical Physics Letters, 15 (2). pp. 171-178. ISSN 0009-2614. doi:10.1016/0009-2614(72)80143-X. https://resolver.caltech.edu/CaltechAUTHORS:20180731-132413916
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Abstract
Ab initio calculations have been carried out for the T(^(3)B_(1u)) and V(^(1)B_(1u)) states of ethylene in a planar nuclear configuration. A “double-zeta” gaussian basis, augmented by diffuse functions, was used. A wide variety of configuration interaction wavefunctions (including as many as 1605 configurations), optimized by the iterative natural orbital method, were computed. The calculations predict the ^(1)B_(1u) state to lie 3.8 – 4.1 eV above the 3B1u state. The spatial extent of the triplet state is that of a normal valence state with (x2) ≈ 12 bohr^2. The singlet state, on the other hand, is found to be quite diffuse or Rydberg-like, (x^2) ≈ 35 bohr^2; electron correlation was found to decrease (x^2) by 30% from the Hartree - Fock value (52 bohr^2). This result is not consistent with simple notions concerning π-electron theory.
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| Additional Information: | © 1972 Published by Elsevier B.V. Received 28 March 1972. Revised manuscript received 4 May 1972. We thank Drs. V. McKoy, R.J. Buenker, A.J. Merer, K. Morokuma, A. Moscowitz, R.S. Mulliken, K. Ohno, S.D. Peyerimhoff, R.M. Pitzer, J. Priestly, G.W. Robinson, G.A. Segal, L Shavitt, J.L. Whitten and N.W. Winter for helpful discussions. Bender - Work performed under the auspices of the U.S. Atomic Energy Commission. Arthur Amos Noyes Laboratory of Chemical Physics Contribution No. 4436. Schaefer - Supported by the National Science Foundation, Grant No. GP-31974. Goddard - Supported by the National Science Foundation, Grant No. GP-15423. Hunt - NDEA Fellow. | |||||||||
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| Issue or Number: | 2 | |||||||||
| DOI: | 10.1016/0009-2614(72)80143-X | |||||||||
| Record Number: | CaltechAUTHORS:20180731-132413916 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180731-132413916 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 88387 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Donna Wrublewski | |||||||||
| Deposited On: | 31 Jul 2018 20:40 | |||||||||
| Last Modified: | 16 Nov 2021 00:26 |
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