TY - JOUR
T1 - Adjacent keto and enol groups in photochemistry of a cyclic molecule
T2 - Products, mechanisms and dynamics
AU - Shemesh, Dorit
AU - Salomon, Ronnie
AU - Kim, Stephanie Hyejin
AU - Tyndall, Geoffrey S.
AU - Nizkorodov, Sergey A.
AU - Gerber, R. Benny
N1 - Publisher Copyright:
© 2018 Elsevier B.V.
PY - 2018/11/14
Y1 - 2018/11/14
N2 - The photochemistry of carbonyl compounds is of considerable atmospheric importance, but the mechanisms and dynamics are often unknown. Here, we explore these topics for a system with adjacent keto and enol chromophoric groups. The photochemistry in the S1 and S2 states of the most stable tautomer of 1,2-cyclohexanedione, is studied theoretically using molecular dynamics simulations with a semi-empirical excited-state potential. Results are compared with experiments. The main results are: (1) Calculations provide an interpretation of the measured absorption spectrum. (2) There is good agreement between the predicted and experimental photoproducts. (3) Agreement with experiments on the products suggests the latter can be predicted without treating non-adiabatic transitions. (4) The mechanisms of formation of the products are predicted by the simulations. (5) The adjacent keto-enol system is found to be photochemically very different from the pure keto one.
AB - The photochemistry of carbonyl compounds is of considerable atmospheric importance, but the mechanisms and dynamics are often unknown. Here, we explore these topics for a system with adjacent keto and enol chromophoric groups. The photochemistry in the S1 and S2 states of the most stable tautomer of 1,2-cyclohexanedione, is studied theoretically using molecular dynamics simulations with a semi-empirical excited-state potential. Results are compared with experiments. The main results are: (1) Calculations provide an interpretation of the measured absorption spectrum. (2) There is good agreement between the predicted and experimental photoproducts. (3) Agreement with experiments on the products suggests the latter can be predicted without treating non-adiabatic transitions. (4) The mechanisms of formation of the products are predicted by the simulations. (5) The adjacent keto-enol system is found to be photochemically very different from the pure keto one.
KW - 1,2-Cyclohexanedione
KW - 2-Hydroxy-2-cyclohexen-1-one
KW - Molecular dynamics for excited states
KW - Photochemistry
KW - Reaction mechanisms
KW - Semi-empirical quantum-chemical potentials
UR - http://www.scopus.com/inward/record.url?scp=85054324945&partnerID=8YFLogxK
U2 - 10.1016/j.chemphys.2018.07.045
DO - 10.1016/j.chemphys.2018.07.045
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AN - SCOPUS:85054324945
SN - 0301-0104
VL - 515
SP - 177
EP - 186
JO - Chemical Physics
JF - Chemical Physics
ER -