The purpose of this paper is to study the model [4 + 4] photocycloaddition of butadiene + butadiene by using direct dynamics calculations-with no geometric constraints-to describe motion along excited-state reaction paths and subsequent decay to the ground state. We use the molecular mechanics-valence bond (MMVB) potential, which is calibrated against previous CASSCF calculations for this system (Bearpark, M. J.; Deumal, M.; Robb, M. A.; Vreven, T.; Yamamoto, N.; Olivucci, M.; Bernardi, F. J. Am. Chem. Sec. 1997, 119, 709-718). Our dynamics calculations show that efficient nonradiative decay of butadiene + butadiene in the presence of two different S-1/S-0 conical intersections can account for the formation of many products. The major product predicted by MMVB is consistent with the limited experimental data available.
Deumal, M., Bearpark, M.J., Smith, B.R., Olivucci, M., Bernardi, F., Robb, M.A. (1998). Product Distributions from Molecular Mechanics−Valence Bond Dynamics: Modeling Photochemical [4 + 4] Cycloadditions. JOURNAL OF ORGANIC CHEMISTRY, 63(14), 4594-4600 [10.1021/jo972111v].
Product Distributions from Molecular Mechanics−Valence Bond Dynamics: Modeling Photochemical [4 + 4] Cycloadditions
Olivucci, Massimo;
1998-01-01
Abstract
The purpose of this paper is to study the model [4 + 4] photocycloaddition of butadiene + butadiene by using direct dynamics calculations-with no geometric constraints-to describe motion along excited-state reaction paths and subsequent decay to the ground state. We use the molecular mechanics-valence bond (MMVB) potential, which is calibrated against previous CASSCF calculations for this system (Bearpark, M. J.; Deumal, M.; Robb, M. A.; Vreven, T.; Yamamoto, N.; Olivucci, M.; Bernardi, F. J. Am. Chem. Sec. 1997, 119, 709-718). Our dynamics calculations show that efficient nonradiative decay of butadiene + butadiene in the presence of two different S-1/S-0 conical intersections can account for the formation of many products. The major product predicted by MMVB is consistent with the limited experimental data available.
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https://hdl.handle.net/11365/32706
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