Exploiting quantum interference effects for the determination of the absolute orientation of an electronic transition moment vector in an isolated molecule

Plusquellic, David F.; Pratt, David W.
December 1992
Journal of Chemical Physics;12/15/1992, Vol. 97 Issue 12, p8970
Academic Journal
Quantum interference effects have been observed in the O00 band of the fully resolved S1←S0 fluorescence excitation spectrum of the hydrogen bonded complex of trans-2-naphthol with ammonia (t-2HNA). The effects owe their origin to the simultaneous existence of (1) ab hybrid band character in the spectrum; (2) perturbations in the spectrum that are produced by a coupling of overall rotation with the hindered internal rotation of the attached NH3 group; and (3) low barriers along the torsional coordinate in both electronic states. Analysis of the resulting interference patterns makes possible an unambiguous determination of both the magnitude and the sign of the orientation of the transition moment vector with respect to the a inertial axis in t-2HNA, θTM=-66±2°. Comparison of this result with that for the S1←S0 transition of the bare molecule shows that the orientation of its transition moment in the molecular frame is unaffected by complex formation. Additionally, symmetry-based arguments are given that may be used to predict the existence of quantum interference effects of this type in other systems.


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