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Nonempirical Calculations on Excited States: The Formaldehyde Molecule

Dunning, Thomas H., Jr. and McKoy, Vincent (1968) Nonempirical Calculations on Excited States: The Formaldehyde Molecule. Journal of Chemical Physics, 48 (11). pp. 5263-5270. ISSN 0021-9606. doi:10.1063/1.1668203.

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A series of calculations on the excited states of formaldehyde using excitation operator techniques are presented. As in ethylene, the effect of sigma–pi interaction on the "pi-->pi*"(1A1) excitation is rather large, decreasing the calculated excitation energy from 14.89 to 12.03 eV and the oscillator strength from 1.01 to 0.30. The coupling has little effect on the corresponding triplet state (3A1). The next higher approximation reduces the excitation energy to 11.22 eV and the oscillator strength to 0.21. The effect of the coupling on the "n-->pi*"(1,3A2) excitations is not as large as that for the 1A1 state, lowering the excitation energies for both the singlet and triplet by ~0.5 eV. Similar results were obtained for the "sigma-->pi*"(1,3B1) excitations. Trends are observed in calculations on corresponding states in ethylene and formaldehyde. Numerous one-electron properties are calculated for the excited states. The results are in moderate agreement with experiment; a major source of error probably arises from the use of an unoptimized, minimum basis set LCAO(STO)–MO–SCF wavefunction.

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Additional Information:© 1968 American Institute of Physics. Received 1 November 1967. We wish to thnak Dr. R.M.Pitzer and Mr. Soe Aung for the results of the LCAO-MO-SCF calculation on formaldehyde and Dr. W.E. Palke and Dr. W.A. Goddard for numerous helpful discussions. One of us (T.H.D.) thanks the National Science Foundation for fellowship support. This work was supported in part by a grant from the NSF (GP 6965). [T.H.D., Jr. was a] National Science Foundation Predoctoral Fellow, 1965-1968. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 3593.
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National Science FoundationGP 6965
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Arthur Amos Noyes Laboratory of Chemical Physics3593
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Deposited On:30 Oct 2008 20:14
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