A Conical Intersection Influences the Ground State Rearrangement of Fulvene to Benzene

Carpenter, Barry K.; Ellison, G. Barney; Nimlos, Mark R.; Scheer, Adam M.

doi:10.1021/acs.jpca.2c00038

Title: A Conical Intersection Influences the Ground State Rearrangement of Fulvene to Benzene

Journal Article · 21 February 2022 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.2c00038 · OSTI ID:1854586

^[1];

^[2];

^[3]; Scheer, Adam M. ^[4]

Cardiff Univ. (United Kingdom)
Univ. of Colorado, Boulder, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Recurve Inc., Fort Collins, CO (United States)

The rearrangement of fulvene to benzene is believed to play an important role in the formation of soot during hydrocarbon combustion. Previous work has identified two possible mechanisms for the rearrangement-a unimolecular path and a hydrogen-atom-assisted, bimolecular path. Computational results to date have suggested that the unimolecular mechanism faces a barrier of about 74 kcal/mol, which makes it unable to compete with the bimolecular mechanism under typical combustion conditions. This computed barrier is about 10 kcal/mol higher than the experimental value, which is an unusually large discrepancy for modern electronic structure theory. In the present work, we have reinvestigated the unimolecular mechanism computationally, and we have found a second transition state that is approximately 10 kcal/mol lower in energy than the previously identified one and, therefore, in excellent agreement with the experimental value. The existence of two transition states for the same rearrangement arises because there is a conical intersection between the two lowest singlet states which occurs in the vicinity of the reaction coordinates. The two possible paths around the cone on the lower adiabatic surface give rise to the two distinct saddle points. The lower barrier for the unimolecular mechanism now makes it competitive with the bimolecular one, according to our calculations. In support of this conclusion, we have reanalyzed some previous experimental results on anisole pyrolysis, which leads to benzene as a significant product and have shown that the unimolecular and bimolecular mechanisms for fulvene ? benzene must be occurring competitively in that system. Finally, we have identified that similar conical intersections arise during the isomerizations of benzofulvene and isobenzofulvene to naphthalene.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1854586

Report Number(s):: NREL/JA-2800-82361; MainId:83134; UUID:4b34199e-63f6-4e51-b35d-c33a3b3b2592; MainAdminID:64021

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 8 Vol. 126; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anisole pyrolysis
benzene
conical intersection
hydrocarbon combustion
unimolecular mechanism

Title: A Conical Intersection Influences the Ground State Rearrangement of Fulvene to Benzene

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