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Multiconfiguration wavefuntions for the lowest (ππ*) excited states of ethylene

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.

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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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Goddard, William A., III0000-0003-0097-5716
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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Deposited By: Donna Wrublewski
Deposited On:31 Jul 2018 20:40
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