Location of the charge and geometric components of soliton waves in cations of unsymmetrical conjugated systems

A quantum-chemical investigation into the location and form of solitons in the cations of unsymmetrical polymethine systems was undertaken. It was shown that the introduction of one terminal group (electron-donating or electron-accepting) with intrinsic level outside the energy gap of the main chromophore leads to displacement of the charge and geometric waves without substantial distortion of their form; the introduction of an amino group with a high level for the unshared electron pair is accompanied by displacement of the solitons to the end of the conjugation chain, so that half of the soliton wave projects onto the molecule. In unsymmetrical polymethine cations with two nitrous groups the geometric soliton is closer to the less basic residue; replacement of one terminal residue by a methoxy group moves the position of the soliton to the end of the chromophore. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 4, pp. 221–227, July–August, 2008.