Abstract
Optimized geometries and relative energies for three states of the C4, molecule have been obtained from single-reference configuration interaction (SRCI) calculations. The 1∑g + acetylenic form correlates with two ground state1∑g + C2molecules, from which it can be formed without activation. The1∑g + state, however, is calculated to lie approximately 25 kcal above the 3∑g − state. At the SRCI level, a rhombic form is calculated to lie 1.1 kcal below the triplet form; consideration of the Davidson correction reduces this difference to 0.4 kcal, while more complete basis sets are expected to increase the difference only by about 0.2 kcal. Consideration of these effects and difference in zero-point energy leads to a final estimated splitting of 1.2 kcal, favoring the rhombus. To aid the determination of the ground state, preliminary estimates of the lowest optical transitions were obtained from SRCI calculations and vibrational frequencies were obtained from SCF calculations. Comparison of the calculated results with experimentally obtained spectra suggest the possibility that both the linear triplet and the rhombus may have already been observed.
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© 1986 D. Reidel Publishing Company
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Ritchie, J.P., King, H.F., Young, W.S. (1986). Theoretical Studies of the C4 Molecule. In: Rentzepis, P.M., Capellos, C. (eds) Advances in Chemical Reaction Dynamics. NATO ASI Series, vol 184. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4734-4_19
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DOI: https://doi.org/10.1007/978-94-009-4734-4_19
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