Abstract
Chemically generated electronically excited species are of interest because of potential applications in short wavelength chemical lasers. Thermal decomposition of FN3 using ~1-J/cm2 CO2 laser pulses in the presence of SF6 has generated metastable NF(a) very efficiently.1 This is attributed to a low energy barrier to dissociation arising from the extremely weak FN—N2 bond and to a spin constraint which allows only singlet dissociation products from the ground state FN3. Since these considerations also apply to CIN3 its decomposition is expected to yield NCl(a) efficiently. Coproduction of NCl(a) along with NF(a) may then be used to pump lasants such as NF(b) or IF(B) by resonant energy pooling reactions. Therefore, dissociation of CIN3 has been investigated in similar conditions suitable to FN3 dissociation. The products were found by emission spectroscopy to be NCl(a) and NCl(b). Time-resolved UV absorption of CIN3 showed that the rate coefficient of CIN3 dissociation is approximately half of that for FN3 implying a higher dissociation energy barrier for CIN3. This result is expected because of lower electronegativity of the Cl-atom and the consequently stronger CIN—N2 bond. The yield of NCl(a) radicals has been found by absolute photometry to be near unity.
© 1990 Optical Society of America
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