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Colussi, A. J.

Publications and source records attributed to Colussi, A. J..

Temperature dependence and mechanism of the reaction between O(3P) and chlorine dioxide

Second-order rate constants for the decay of O(3P) in excess chlorine dioxide, k(II), were measured as a function of total pressure (20-600 Torr argon) and temperature (248-312 K), using flash photolysis-atomic resonance fluorescence. Results indicate that k(II) is pressure dependent with a value, K(b), that is nonzero at zero pressure, and both the third-order rate constant and k(b) have negative temperature dependences.

Colussi, A. J.↗

Induced ClO vacuum ultraviolet fluorescence

Some vibronic transitions of ClO such as G(v-prime = 11 )-X(v-double prime = 10), G(v-prime = 5)-X(v-double prime = 3) and H(v-prime = 4)-X(v-double prime = 2), which promote overtones of X(2pi3/2) to bound Rydberg states, are nearly resonant with the 130.6 nm O-atom emission line and possess sizable Franck-Condon factors. On this basis broadband detection of 'O atom' fluorescence in experiments involving vibrationally excited ClO(X) is ascribed to the radiative decay of ClO(G, H) rather than to the formation of O atoms; these observations raise the probability of monitoring ClO(X; v = 0) by VUV-induced fluorescence.

Colussi, A. J.↗

Thermodynamics of acetylene van der Waals dimerization

Integrated band intensities of the 620/cm absorption in (C2H2)2 are measured by FTIR spectroscopy at constant acetylene pressure between 198 and 273 K. These data, in conjunction with ab initio results for (C2H2)2, are used for the statistical evaluation of the equilibrium constant Kp(T) for acetylene-cluster dimerization. The present results are used to clarify the role of molecular clusters in chemical systems at or near equilibrium, in particular in Titan's stratosphere.

Colussi, A. J.↗

Formation and decay of (3P(J))O atoms in the laser flash photolysis of chlorine dioxide (OClO) at 308 nm

The quantum yields of O(3P(J)) and Cl(2P(3/2)) atoms released in the laser flash photolysis of OClO at 308 and 298 K were determined and the kinetics of the subsequent oxygen atom decay was investigated using time-resolved atomic resonance fluorescence measurements. The results are consistent with the formation of sym-ClO3 having a Delta Hf(ClO3) (formed in the reaction O + OClO + Ar) of 55.6 +/-4 kcal/mol.

Colussi, A. J.↗