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Excited States of Butadiene to Chemical Accuracy: Reconciling Theory and Experiment

Watson, Mark A. and Chan, Garnet Kin-Lic (2012) Excited States of Butadiene to Chemical Accuracy: Reconciling Theory and Experiment. Journal of Chemical Theory and Computation, 8 (11). pp. 4013-4018. ISSN 1549-9618. doi:10.1021/ct300591z.

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We obtain the vertical excitation energies of the notoriously challenging lowest-lying dark and bright excitations of trans-butadiene to chemical accuracy using high-order equation-of-motion coupled-cluster theory. Convergence is demonstrated in both the one-particle basis set (up to augmented quintuple-zeta quality) and the coupled-cluster expansion (including up to connected quadruple excitations) within an incremental scheme. Our best estimates for the bright 1^1(B_u)^+ and dark 2^1(A_g)^– vertical transitions are 6.21 ± 0.02 eV and 6.39 ± 0.07 eV, respectively, establishing definitively that the vertical 11Bu+ transition lies below the 2^1(A_g)^– transition. Our 11Bu+ excitation energy remains significantly higher than the generally cited experimental value of 5.92 eV. To rationalize this difference, we have computed the zero-point vibrational energy corrections, which reduce the theoretical 1^1(B_u)^+ excitation energy to 6.11 eV. We also correct for nonverticality in the experimental value by recomputing the transition as the weighted intensity average of the electron impact energy loss spectra, which gives the range 5.96–6.05 eV. The corrected best theoretical and experimental 1^1(B_u)^+ excitation energies are then in good agreement, resolving a long-standing discrepancy.

Item Type:Article
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Chan, Garnet Kin-Lic0000-0001-8009-6038
Additional Information:© 2012 American Chemical Society. Received: July 11, 2012. Published: September 25, 2012. The authors gratefully acknowledge financial support from the U.S. Department of Energy (DE-FG02-07ER46432), Princeton University, and the Sloan, Dreyfus, and Packard Foundations. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-07ER46432
Princeton UniversityUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
David and Lucile Packard FoundationUNSPECIFIED
Issue or Number:11
Record Number:CaltechAUTHORS:20170125-092628371
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:73705
Deposited By: Donna Wrublewski
Deposited On:25 Jan 2017 20:45
Last Modified:11 Nov 2021 05:20

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