Cluster Ion Thermal Decomposition (I): Experimental Kinetics Study and ab Initio Calculations for HSO 4 - (H 2 SO 4 ) x (HNO 3 ) y
2001; American Chemical Society; Volume: 105; Issue: 48 Linguagem: Inglês
10.1021/jp0124950
ISSN1520-5215
AutoresJoachim Curtius, K. D. Froyd, Edward R. Lovejoy,
Tópico(s)Atomic and Molecular Physics
ResumoRate coefficients for the thermal decomposition of cluster ions of the type HSO4-(H2SO4)x for x = 1−5, HSO4-(HNO3)y for y = 1, 2 and HSO4-H2SO4HNO3 were measured as functions of temperature and pressure in a quadrupole ion trap. The measured decomposition kinetics are in the low-pressure limit or in the fall-off region between the low and high-pressure limits. Moments of inertia and vibrational frequencies of the clusters were obtained via ab initio HF/6-31+G(d) geometry optimizations. Bond energies were determined from analysis of the second-order rate coefficient data for the cluster ions with kinetics in the low-pressure limit. Upper limits of the bond energies were derived for the clusters with kinetics in the fall-off region.
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