Knowledge Bank

Emission spectra obtained from bulk-gas methinophosphide (HCP) have been interpreted through use of a novel algebraic scheme that explicitly takes into account inherent non-rigidity of the molecular $framework.a$ Fluorescence accompanying selective excitation of individual $A~1A\prime \prime -X~\mathrm{<mrow\; data-mjx-texclass="ORD">1</mrow>}\Sigma$ vibronic bands was dispersed under moderate resolution, with the appearance of substantial activity in the $\nu 2$ bending mode reflecting the bent-from-linear nature of the $A~\leftarrow X~$ transition. Aside from providing an economical parameterization for observed patterns of vibrational term energies, the algebraic approach affords a robust and facile means for the quantitative evaluation of multidimensional Franck-Condon factors. These results, as well as subsequent extensions designed to account for non-Condon effects, will be discussed in order to further elucidate the unique structure and dynamics exhibited by participating electronic states.