ELECTRONIC SPECTROSCOPY IN RIGID ORGANIC SOLUTIONS AT HIGH ELECTRIC FIELD STRENGTHS
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Date
1968
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Ohio State University
Abstract
A quasi-static (audio frequency) homogeneous electric field can be considered as a well defined perturbation in the molecular Hamiltonian. When such a perturbation is sufficiently strong, one can expect to observe a number of significant changes in molecular properties. Two such effects in the electronic spectra are studied in a rigid solution in 3-methylpentane at liquid nitrogen temperature. In this environment molecules are not capable of free rotation. This gives rise to spectral changes different from those observed in liquid solutions or in gases. First we report a determination of a change in dipole moment upon excitation in azulene to the $^{1}A_{1} (2)$ state (0-0-transition around $3530 {\AA}$). Second, the electric field may perturb the spin-orbit coupling operator and open a new decay channel for the lowest triplet state, thus shortening the phosphorescence lifetime. An effect found in phenanthrene is discussed in these terms. A rigid solution allows the use of considerably higher electric fields than either the liquid or the gas phase. The fields used range up to $5 \times 10^{5} Vcm^{-1}$.
Description
This work has been supported in part by a grant from the Natioanl Science Foundation and in part by the Materials Science Center at Cornell University.
Author Institution: Chemistry Department, Cornell University
Author Institution: Chemistry Department, Cornell University