Monte Carlo classical dynamical study of the Cl + Cl2 and I + I2 systems: Vibrational relaxation and atom-exchange reactions

Abstract

Articles you may be interested inEffects of translational, rotational, and vibrational energy on the dynamics of the D+H2 exchange reaction. A classical trajectory study J. Chem. Phys. 94, 7991 (1991); 10.1063/1.460133 Vibrational relaxation of Cl2 by HCl and DCl and selfrelaxation of HCl and DCl: A Monte Carlo quasiclassical trajectory study J. Chem. Phys. 66, 2545 (1977); 10.1063/1.434250On the thermal rate coefficient and activation energy of the I+I2 atomexchange reactionThe Monte Carlo quasiclassical trajectory method is used to investigate the atom-exchange reactions and the vibrational relaxation in the systems CI + CI 2 and 1+1 2 , The CI + CI 2 system is examined over the temperature range 500-1500'K and initial vibrational states v =0, I, 3, 7, and 14, and the 1+12 system is examined over the temperature range 700-1500'K and initial vibrational levels v =0, I, 7, 10, 12, and 14. London equation potential-energy surfaces are employed; the energy barner to linear configuration atom exchange is zero for CI+CI 2 and about 5.9 kcallmole for 1+12' The rates of atom exchange for both CI + CI 2 and 1 + 12 are calculated as a function of temperature and initial vibrational state. Vibrational relaxation rate coefficients are calculated for individual transitions v ~v' for both reactive and nonreactive collisions. It is found that both nonreactive collisions and atom-exchange reactions contribute to the vibrational relaxation.

Dissociation energy of molecules in dense gases

“…Similar values, 2968 and 2666 K, respectively, were obtained by Thompson [21] from the Monte Carlo trajectory calculations, and by Bunker and Davidson [22] from thermodynamic considerations. Geometrical average of the potential well depths obtained by Thompson and by Bunker and Davidson gives c, /k =2813 K. The studies of Blake and Burns [20] and of Thompson [21] suggest that Lennard-Jones potential with parameters discussed above is an acceptable approximation of the overall forces dominating the I+I2 interaction, even though it ignores such effects as, for example, the AD (r ) =g, exp[a( r, *r ) ], Therefore the values of hD for the Ar-N2 interactions were obtained from the formula (55). Parameters for the interaction potentials for the Ar-N2 system were taken from Ref.…”

Direct observation and reactions of Cl3 radical

“…[17][18][19][20][21][22][23] Emission spectra attributable to Cl 3 were observed by Kawasaki et al 14 and Wright et al 15 These data were in reasonable agreement with each other. An IR spectrum of Cl 3 in a Kr matrix was reported by Nelson and Pimentel.…”

Photolysis of Matrix-Isolated HCl−Cl2 Complexes: Electronic Absorption and Emission Spectra Provisionally Assigned to Cl3

“…Following this work, Wright et al suggested that a 370−420 nm emission band, observed when Cl 2 was photodissociated under relatively high-pressure conditions, might also originate from Cl 3 . In parallel with the experimental efforts there have been many attempts to calculate potential energy surfaces for trihalogens using ab-initio ,− and semiempirical methods. ,− …”