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INTERDEPENDENCE OF GUEST RADIATIONLESS TRANSITIONS AND LOCALIZED PHONON STRUCTURE: NH AND ND ($A^{3}\Pi$) IN RARE GAS LATTICES

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/9506

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Title: INTERDEPENDENCE OF GUEST RADIATIONLESS TRANSITIONS AND LOCALIZED PHONON STRUCTURE: NH AND ND ($A^{3}\Pi$) IN RARE GAS LATTICES
Creators: Bondybey, V. E.; Brus, L. E.
Issue Date: 1975
Abstract: NH and ND ($A^{3}\Pi$) radicals in rare gas lattices were studied by their time and wavelength resolved fluorescence. The temperature dependence of the localized phonon structure indicates that the ground $X^{3}\Sigma^{-}$ state undergoes near free rotation, while the excited $A^{3}\Pi$ state librates. A strong violation of the energy gap law for vibrational relaxation is observed with NH rates 10$-10^{2}$ higher than in ND. The vibrational relaxation rates are independent of temperature for $T < 25 ^{\circ} K$ in Ar and $< 37 ^{\circ} K$ in Kr; however, lifetimes of several $A^{3}\Pi$ vibrational levels show a dramatic temperature dependence attributed to intersystem crossing into $^{1}\Delta$. We propose that the localized near free rotation mode accepts the energy during vibrational relaxation, while delocalized Lattice phonons accept energy during intersystem crossing.
URI: http://hdl.handle.net/1811/9506
Other Identifiers: 1975-TH-05
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