skip to main content

Title: Vibrational coherences in charge-transfer dyes: A non-adiabatic picture

Essential-state models efficiently describe linear and nonlinear spectral properties of different families of charge-transfer chromophores. Here, the essential-state machinery is applied to the calculation of the early-stage dynamics after ultrafast (coherent) excitation of polar and quadrupolar chromophores. The fully non-adiabatic treatment of coupled electronic and vibrational motion allows for a reliable description of the dynamics of these intriguing systems. In particular, the proposed approach is reliable even when the adiabatic and harmonic approximations do not apply, such as for quadrupolar dyes that show a multistable, broken-symmetry excited state. Our approach quite naturally leads to a clear picture for a dynamical Jahn-Teller effect in these systems. The recovery of symmetry due to dynamical effects is however disrupted in polar solvents where a static symmetry lowering is observed. More generally, thermal disorder in polar solvents is responsible for dephasing phenomena, damping the coherent oscillations with particularly important effects in the case of polar dyes.
Authors:
; ;  [1] ; ;  [1] ;  [2]
  1. Dipartimento di Chimica, Università degli studi di Parma, Parco Area delle Scienze 17/A, 43124 Parma (Italy)
  2. (Italy)
Publication Date:
OSTI Identifier:
22310758
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; APPROXIMATIONS; EXCITATION; EXCITED STATES; JAHN-TELLER EFFECT; OSCILLATIONS; SOLVENTS; SYMMETRY BREAKING