Manz, J. and Proppe, B. and Schmidt, B. (2002) TimeResolved Dual Fluorescence of 1Phenylpyrrole in Acetonitrile: Molecular Dynamics Symulations of Solvent Response to Twisted Intramolecular Charge Transfer. Phys. Chem. Chem. Phys., 4 (10). pp. 18761881.

PDF
 Published Version
Available under License Creative Commons Attribution Noncommercial. 141kB 
Official URL: http://dx.doi.org/10.1039/b109488b
Abstract
The real time dynamics of solvation of 1phenylpyrrole (PhPy) in acetonitrile (ACN) upon electronic excitation is investigated by means of nonequilibrium molecular dynamics simulations. The interaction is modeled by empirical intermolecular pair potentials using partial charges and intramolecular torsional potentials from high level ab initio calculations of ground and excited states of PhPy. The intramolecular torsional motion following sudden excitation from the twisted ground state to the 21B charge transfer state is strongly damped by the viscous ACN solvent leading to a nearexponential approach of the perpendicular conformation on a timescale of about 5...10 ps. The intermolecular dynamics is characterized by rapid reorientation of the solvent molecules on a time scale of 100 fs followed by weak quasicoherent librations. The solvatochromatic red shift of the charge transfer state with respect to the locally excited 11B state results in dual fluorescence thus supporting the twisted intramolecular charge transfer (TICT) mechanism for PhPy in a polar solvent.
Item Type:  Article 

Subjects:  Mathematical and Computer Sciences > Mathematics 
Divisions:  Department of Mathematics and Computer Science > Institute of Mathematics Department of Mathematics and Computer Science > Institute of Mathematics > BioComputing Group 
ID Code:  77 
Deposited By:  Admin Administrator 
Deposited On:  03 Jan 2009 20:20 
Last Modified:  03 Mar 2017 14:39 
Repository Staff Only: item control page