title: Modulating unimolecular charge transfer by exciting bridge vibrations.
abstract: Ultrafast UV-vibrational spectroscopy was used to investigate how vibrational excitation of the bridge changes photoinduced electron transfer between donor (dimethylaniline) and acceptor (anthracene) moieties bridged by a guanosine-cytidine base pair (GC). The charge-separated (CS) state yield is found to be lowered by high-frequency bridge mode excitation. The effect is linked to a dynamic modulation of the donor-acceptor coupling interaction by weakening of H-bonding and/or by disruption of the bridging base-pair planarity.
authors.affiliation: Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.
authors.forename: Zhiwei
authors.initials: Z
authors.lastname: Lin
authors.forename: Candace M
authors.initials: CM
authors.lastname: Lawrence
authors.forename: Dequan
authors.initials: D
authors.lastname: Xiao
authors.forename: Victor V
authors.initials: VV
authors.lastname: Kireev
authors.forename: Spiros S
authors.initials: SS
authors.lastname: Skourtis
authors.forename: Jonathan L
authors.initials: JL
authors.lastname: Sessler
authors.forename: David N
authors.initials: DN
authors.lastname: Beratan
authors.forename: Igor V
authors.initials: IV
authors.lastname: Rubtsov
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry* / Q000528:radiation effects; D000873:Anthracenes / Q000737:chemistry* / Q000528:radiation effects; D003562:Cytidine / Q000737:chemistry / Q000528:radiation effects; D004579:Electron Transport; D006151:Guanosine / Q000737:chemistry / Q000528:radiation effects; D006860:Hydrogen Bonding; D007700:Kinetics; D008956:Models, Chemical; D015394:Molecular Structure; D010777:Photochemistry; D013056:Spectrophotometry, Ultraviolet; D014732:Vibration
chemical_list: D000814:Aniline Compounds; D000873:Anthracenes; D006151:Guanosine; D003562:Cytidine; C015157:N,N-dimethylaniline; C034020:anthracene