ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The reaction of sulfur atom and nitrogen dioxide is studied by B3LYP/cc-pVTZ method. The potential energy surfaces of the reaction on several electronic states are computed by time-dependent density functional theory (TD–DFT). The complexes of the precursor of sulfur atom, OCS and CS2, and NO2 are also studied to probe all possible reactive routes. The possible products in the ground state are SNO2, SONO, a mixture of SO and NO, as well as cis- and trans-OSNO. Calculations show that the most possible product is SNO2 because it is the product of a barrierless reaction and is trapped in a well of 34 kcal/mol. Even this most probable product, SNO2, might not be detected in matrix-isolation experiment for the precursor of sulfur atom chelates with NO2 and the formation of SNO2 is directionally prohibited. Other products are not likely to be generated in matrix-isolation experiment from the ground state of sulfur atom and NO2 since the barrier of 12 kcal/mol obstructs the reaction route. In the same experimental condition, products other than SNO2 are probably initiated with singlet sulfur. The calculation suggests that the sulfur atom in the 1D state attacks the oxygen atom of NO2 in the 2A1 state, then reacts without barrier, and after a crossing and quenching falls into the lowest 2A′ state around the geometry of a transition structure in the ground state. Afterward, the reaction proceeds to yield the products SO, NO, cis-OSNO, and trans-OSNO. This reaction path bypasses the formation of SNO2; thus, when the sulfur atom is in the 1D excited state, the SNO2 will not be observed. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1405119
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