Isomers of SO2: Infrared absorption of SOO in solid argon

Abstract

Articles you may be interested inComment on ''Infrared spectrum and theoretical study of the dinitrogen pentoxide molecule (N2O5) in solid argon'' [Sulfur dioxide ͑OSO͒ isolated in solid argon at 13 K was irradiated with light at 193 nm from an ArF excimer laser. Weak absorption lines at 1006.1, 1004.7, and 739.9 cm Ϫ1 observed after photolysis are assigned to sulfur superoxide ͑SOO͒; the doublet near ϳ1005 cm Ϫ1 is due to matrix site splitting. The assignments are based on results from 18 O-isotopic experiments. Calculations using the B-P86 and the B3-LYP density-functional methods were made for three isomers of OSO; energies, structures, vibrational wave numbers, and infrared intensities were predicted for each species. Although observed line positions are nearly identical to those predicted with theory for cyclic-SO 2 , experimental relative IR intensities and 18 O-isotopic shifts agree with those predicted for SOO. The mechanism of formation of SOO in a matrix cage is discussed.

Experimental and theoretical investigations of rate coefficients of the reaction S(3P)+O2 in the temperature range 298–878 K

“…The existence of intermediate SOO is supported by its infrared absorption spectrum recorded after photolysis with laser radiation at 193 nm of an Ar matrix sample containing SO 2 . 12 Craven and Murrell performed quasiclassical trajectory ͑QCT͒ calculations and predicted a rate coefficient of (1.67Ϯ0.17)ϫ10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 for reaction ͑1͒ at 298 K, in satisfactory agreement with experiment. 13,14 All trajectories show a common mechanism in which an initial SOO intermediate is formed, followed by rapid isomerization to OSO, which subsequently dissociates to OϩSO.…”

“…5. Predicted vibrational wave numbers and rotational constants as well as available experimental data [43][44][45][46][47] for the species involved are discussed and summarized in Table 4 of Ref. 38.…”

Excited Electronic States of the Cyclic Isomers of O3 and SO2

“…23,36,37 In 1995, Kellogg et al used the CCSD(T) method with a triple-basis set and obtained a value of 4.52 eV (104 kcal/mol) for this energy difference. 36 Ivanic et al obtained a value of 97.2 kcal/mol using FORS.…”

“…29,32,33 Influenced by the studies of Shih et al 8 on cyclic-O 3 , the possibility of a low-lying ring isomer of SO 2 began to be investigated. 23,[34][35][36][37] Kellogg et al found that all three SO 2 isomers were minima at the MRCI level of theory. 36 While the energy difference between O 3 and cyclic-O 3 is on the order of 30 kcal/mol, the difference between the open and ring isomers of SO 2 is calculated to be around 100 kcal/mol.…”

Trends of the bonding effect on the performance of DFT methods in electric properties calculations: A pattern recognition and metric space approach on some XY2 (X = O, S and Y = H, O, F, S, Cl) molecules

“…The ozone's ring form had been first observed as a minimum in the potential energy surface by Ruedenberg and coworkers41 back in 1994 and only recently Plass and coworkers42 provided the first experimental evidence of its existence by detecting the ring form in deficiencies of magnesium oxide surface reconstructions. On the other hand, a number of recent studies has been devoted to the ring structure of sulfur dioxide43, 44 and valuable information for its geometry and vibrational frequencies can be found in studies by Kellogg and Schäffer 45, 46…”