TY - JOUR
T1 - Cyclooctatetraene computational photo- and thermal chemistry
T2 - A reactivity model for conjugated hydrocarbons
AU - Garavelli, Marco
AU - Bernardi, Fernando
AU - Cembran, Alessandro
AU - Castaño, Obis
AU - Frutos, Luis Manuel
AU - Merchán, Manuela
AU - Olivucci, Massimo
PY - 2002/11/20
Y1 - 2002/11/20
N2 - We use ab initio CASSCF and CASPT2 computations to construct the composite multistate relaxation path relevant to cycloocta-1,3,5,7-tetraene singlet photochemistry. The results show that an efficient population of the dark excited state (S 1) takes place after ultrafast decay from the spectroscopic excited state (S 2). A planar D 8h-symmetric minimum represents the collecting point on S 1. Nonadiabatic transitions to S 0 appear to be controlled by two different tetraradical-type conical intersections, which are directly accessible from the S 1 minimum following specific excited-state reaction paths. The higher-energy conical intersection belongs to the same type of intersections previously documented in linear and cyclic conjugated hydrocarbons and features a triangular -(CH) 3- kink. This point mediates both cis → trans photoisomerization and cyclopropanation reactions. The lowest energy conical intersection has a boat-shaped structure. This intersection accounts for production of semibullvalene or for double-bond shifting. The mapping of both photochemical and thermal reaction paths (including also Cope rearrangements, valence isomerizations, ring inversions, and double-bond shifting) has allowed us to draw a comprehensive reactivity scheme for cyclooctatetraene, which rationalizes the experimental observations and documents the complex network of photochemical and thermal reaction path interconnections. The factors controlling the selection and accessibility of a number of conjugated hydrocarbon prototype conical intersections and ground-state relaxation channels are discussed.
AB - We use ab initio CASSCF and CASPT2 computations to construct the composite multistate relaxation path relevant to cycloocta-1,3,5,7-tetraene singlet photochemistry. The results show that an efficient population of the dark excited state (S 1) takes place after ultrafast decay from the spectroscopic excited state (S 2). A planar D 8h-symmetric minimum represents the collecting point on S 1. Nonadiabatic transitions to S 0 appear to be controlled by two different tetraradical-type conical intersections, which are directly accessible from the S 1 minimum following specific excited-state reaction paths. The higher-energy conical intersection belongs to the same type of intersections previously documented in linear and cyclic conjugated hydrocarbons and features a triangular -(CH) 3- kink. This point mediates both cis → trans photoisomerization and cyclopropanation reactions. The lowest energy conical intersection has a boat-shaped structure. This intersection accounts for production of semibullvalene or for double-bond shifting. The mapping of both photochemical and thermal reaction paths (including also Cope rearrangements, valence isomerizations, ring inversions, and double-bond shifting) has allowed us to draw a comprehensive reactivity scheme for cyclooctatetraene, which rationalizes the experimental observations and documents the complex network of photochemical and thermal reaction path interconnections. The factors controlling the selection and accessibility of a number of conjugated hydrocarbon prototype conical intersections and ground-state relaxation channels are discussed.
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U2 - 10.1021/ja020741v
DO - 10.1021/ja020741v
M3 - Article
C2 - 12431107
AN - SCOPUS:0037146062
SN - 0002-7863
VL - 124
SP - 13770
EP - 13789
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 46
ER -