the dynamics of excited state structural relaxation of 4-dimethylaminobenzonitrile (dmabn) and related compounds激发态的动力学结构弛豫4-dimethylaminobenzonitrile(dmabn)和相关化合物.pdfVIP

Hindawi Publishing Corporation International Journal of Photoenergy Volume 2006, Article ID 81896, Pages 1–6 DOI 10.1155/IJP/2006/81896 The Dynamics of Excited State Structural Relaxation of 4-Dimethylaminobenzonitrile (DMABN) and Related Compounds Valery Volchkov, Lyubov’ Uzhinova, and Boris Uzhinov Department of Chemistry, Lomonosov Moscow State University, 119992 Moscow, Russia Received 29 September 2003; Revised 19 July 2005; Accepted 25 July 2005 The excited state structural relaxation of 4-dimethylaminobenzenes with various para -acceptor substituents having double-band emission, local excited (LE) and charge transfer (CT), has been investigated. Fluorescence measurements at different temperatures and in different solvents have confirmed the existence of viscosity-dependent, temperature, and polarity-activated relaxation. The kinetics analysis has shown that the radiative deactivation rate constants of the individual LE and CT states differ by 7–112-fold. The dipole moment changes at the excitation for CT states are significantly larger than those for LE states. The spectral-kinetics behavior of compounds studied agrees with the models A → A∗ → B∗ or A → A∗ ↔ B∗, where A∗ is the local excited planar and B∗ is the relaxed twisted state of the molecule. The rate constants of the twisted state formation have been calculated in the temperature range 293–77 K. The activation energies of forward process for compounds studied have been estimated. Copyright © 2006 Valery Volchkov et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 1. INTRODUCTION