Excited state hydrogen atom transfer in micro-solvated dicoumarol: A TDDFT/EFP1 study.

Abstract

Ground (S0) and excited (S1) state properties of dicoumarol (DC) are investigated by applying density functional theory (DFT) and time dependent DFT (TDDFT) interfacing with the effective fragment potential (EFP) method of solvation. Benzene and pyrone rings of the each 4-hydroxy coumarin (4HC) moiety are in a plane and these planes are twisted by 180° with respect to each other. Two intra-molecular hydrogen bonds (HB) CO⋯HO exist between the carbonyl (CO) and hydroxyl (OH) groups of different 4HC moieties (4HC-1 and 4HC-2). DC(H2O)3 complex is formed using the original EFP model (EFP1). Four inter-molecular HBs are established by the carbonyl and hydroxyl oxygen atoms of 4HC-1 and 4HC-2 moieties; two HBs with two solvent molecules on one side of the complex and other two HBs with one solvent molecule at the other side. In S1 state, the hydrogen atomtransfer takes place only from the hydroxyl group of 4HC-1 to the carbonyl group of 4HC-2. The natural charge analysis and the modification of HBs manifest the intra-molecular charge transfer (ICT) from one 4HC moiety to another. Theoretical and experimental studies of the absorption spectra, and the theoretical study of potential energy curves of OH bonds at both S0 and S1 states affirm the hydrogen atom transfer from the hydroxyl group of 4HC-1 to the carbonyl group of 4HC-2 moiety.