The Journal of Physical Chemistry A · 2006 · 65 citations · 37 references
Natural SciencesChemistryPhysicsComputational ChemistryMolecular PhysicsSpectroscopyFluorescence SpectroscopyMolecular Excited StatesMolecular SpectroscopyPhotochemistryPotential Energy SurfacesCharge-transfer StatesExcited StatesExcited-state Potential Energy SurfacesIntramolecular Electron TransferMolecular Potential Energy SurfacesPhotoinduced Charge TransferPhotophysical MechanismsTime-dependent Density Functional Theory
A donor-acceptor substituted aromatic system (E)-3-(4-Methylamino-phenyl)-acrylic acid methyl ester (MAPAME) has been synthesized, and its photophysical behavior obtained spectroscopically has been compared with the theoretical results. The observed dual fluorescence from MAPAME has been assigned to emission from locally excited and twisted intramolecular charge transfer states. The donor and acceptor angular dependency on the ground and excited states potential energy surfaces have been calculated both in vacuo and in acetonitrile solvent using time dependent density functional theory (TDDFT) and TDDFT polarized continuum model (TDDFT-PCM), respectively. Calculation predicts that a stabilized twisted excited state is responsible for red shifted charge transfer emission.
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