Fluxional electronic spectra

How far carbocation chemistry has evolved from the old solvolysis days is demonstrated by two recent stmcture determinations the IR spectrum of the nonclassical CHs cation has been measured by solvating this unusual species with molecular hydrogen in the gas phase. This slows down the ultrafast fluxional process which so far prevented the recording of vibrational spectra. The cluster ions CH5" (H2)n (n = 1, 2, 3), after mass selection by an ion trap, were then subjected to IR laser spectroscopy/quadrupol mass spectrometry which ultimately yielded the IR absorption. [40] And the benzene cation, formed by removal of one electron from the parent hydrocarbon was shown to possess Deh symmetry by rotation resolved ZEKE-photoelec-tron spectroscopy (Zero Tinetic Energy-PES). [41]... 

Based on the ab initio theory of complex electronic ground state of superconductors, it can be concluded that e-p coupling in superconductors induces the temperature-dependent electronic structure instability related to fluctuation of analytic critical point (ACP - maximum, minimum or saddle point of dispersion) of some band across FL, which results in breakdown of the adiabatic BOA. When ACP approaches FL, chemical potential Pad is substantially reduced to IJ-antiadilJ-ad > Pantiad < b(o). Under these circumstances the system is stabilized, due to the effect of nuclear dynamics, in the antiadiabatic state at broken symmetry with a gap in one-particle spectrum. Distorted nuclear structure, which is related to couple of nuclei in the phonon mode r that induces transition into antiadiabatic state, has fluxional character. It has been shown that until system remains in antiadiabatic state, nonadiabatic polaron - renormalized phonon interactions are... 

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