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Junggil Kim,Kyung Chul Woo,김국기,Minseok Kang,김상규 대한화학회 2022 Bulletin of the Korean Chemical Society Vol.43 No.2
Abstract The πσ*-mediated photochemistry of heteroaromatic molecules has provoked the investigation of the conical intersection dynamics. The Born?Oppenheimer approximation fails at the conical intersection where the S1 (ππ*) and S2 (πσ*) states cross. The nonadiabatic transitions are much influenced by the nuclear configuration of the reactive flux particularly in the curve-crossing region encountered along the reaction pathway. In this article, we focus on the tunneling dynamics of phenols and thiophenols. The O (S)?H bond cleavage occurs via tunneling through the barrier which is dynamically shaped by the upper-lying S1/S2 conical intersection in terms of the couplings at the individual branching planes as well as along the (3N-8) dimensional seam coordinates. State-specific tunneling rates and their interpretation are given for phenol, substituted phenols, thiophenol, ortho-substituted thiophenols, and benzenediols including their 1:1 water clusters. The completely orthogonal modes to the tunneling coordinate are very critical in the dynamic shaping of the reaction barrier.