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- Title
Effects of intermolecular hydrogen bonding on the excited-state proton transfer properties of the cinnamonitrile-methanol complex.
- Authors
Yang, Dapeng; Qi, Ruiquan
- Abstract
The time-dependent density functional theory (TD-DFT) method was used to study the excited-state proton transfer (ESPT) properties of the hydrogen-bonded cinnamonitrile (3TPAN)-methanol (MeOH) complex (3TPAN-MeOH). The intermolecular hydrogen bonds N1···H11 in both the ground state S0 and the excited state S1 were demonstrated by the optimized geometric structures of the hydrogen-bonded 3TPAN-MeOH complex. While in the excited state S3, a new hydrogen bond H11···O1 was formed after the ESPT took place from the hydrogen-bonded MeOH molecule to the 3TPAN moiety. It was demonstrated that the electronic transitions of the S1 states for both the 3TPAN monomer (including the S3 state) and the hydrogen-bonded 3TPAN-MeOH complex should be of a localized-excited (LE) nature on the 3TPAN molecule, while the S3 state of the hydrogen-bonded 3TPAN-MeOH complex should be of charge transfer (CT) character from the hydrogen-bonded MeOH molecule (through O1···H11) to the 3TPAN moiety. The S3-state proton transfer and charge transfer due to the intermolecular hydrogen-bonding interaction should be the reasons for the remarkable redshift (0.91 eV) of the S3-state electronic energy for the hydrogen-bonded 3TPAN-MeOH complex compared with that of the 3TPAN monomer.
- Subjects
HYDROGEN bonding; INTERMOLECULAR interactions; EXCITED states; PROTON transfer reactions; METHANOL; COMPLEX compounds; DENSITY functionals
- Publication
Canadian Journal of Chemistry, 2013, Vol 91, Issue 3, p229
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/cjc-2012-0368