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Optical Properties of Gas‐Phase Tryptophan–Silver Cations: Charge Transfer from the Indole Ring to the Silver Atom
Author(s) -
Antoine Rodolphe,
Tabarin Thibault,
Broyer Michel,
Dugourd Philippe,
Mitrić Roland,
BonačićKoutecký Vlasta
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500495
Subject(s) - chemistry , excited state , absorption spectroscopy , atom (system on chip) , photodissociation , solvation , atomic physics , ion , molecular physics , photochemistry , physics , organic chemistry , quantum mechanics , computer science , embedded system
Abstract 10.1002/cphc.200500495.abs We present a joint experimental and theoretical investigation of the electronic excitation spectra of the tryptophan–silver complex. The photodissociation spectrum of gas‐phase [Trp‐Ag] + was measured from 215 to 330 nm using a quadrupole ion trap coupled to an optical parametric‐oscillator laser. The calculated time‐dependent density functional theory (TD‐DFT) absorption spectra for different prototypes of structures are presented. Low‐energy transitions that are experimentally observed are only calculated for the charge‐solvation (CS) structures. These transitions are a signature of the metal– π interaction in [Trp‐Ag] + . The recorded spectrum is compared to a Boltzmann average of the absorption spectrum obtained from direct molecular dynamics (MD) simulations involving simultaneous transitions to excited states based on semiempirical configuration interaction (CI) calculations. The results demonstrate that charge transfer can be photoinduced from the indole ring to the silver atom.