4.6 Article

Topological characteristics of electron density distribution in SSXY→XSSY (X or Y=F, Cl, Br, I) isomerization reactions

Journal

JOURNAL OF PHYSICAL CHEMISTRY A
Volume 111, Issue 37, Pages 9093-9101

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jp073455k

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The reactions of SSXY to XSSY (X or Y = F, Cl, Br, 1) have been studied at B3LYP/6-311 ++G(2df) and MP2/6-311 ++G(2df) levels based on B3LYP/6-311 ++G(2df) optimized geometries. There are two pathways (X or Y atom transferring) for each reaction of SSXY to XSSY(X or Y = F, Cl, Br, 1). The Atoms in Molecules theory has been applied to analyze the topological characteristics of electron density distribution along the reaction path. (a) The S-S-X or S-S-Y ring structure transition region (STR) is contributed to S(1)-X or S(1)-Y bond formation and S(2)-X or S(2)-Y bond annihilation. The STR and structure transition state (STS) are defined. (b) Comparing the two pathways of each SSXY -> XSSY (X, Y = F, Cl, Br, 1) reaction, X or Y atom transferring, the broader the STR is, the later the STS appears, and the pathway is easier. (c) When X linked to the same S site of a three-member ring (S-S-F, S-S-Cl, S-S-Br, or S-S-I), the ring STR becomes broader and the STS appears later according to the sequence of X = F, Cl, Br, and I. And in these cases, for exothermic reactions, the higher the Delta E(P -> TS1) is, the broader the STR is and the later the STS appears. (d) When the same Y atom linked to different three-member-ring S-S-X, the STR becomes broader and the STS appears later according to the sequence of X = F, Cl, Br, and I in the ring. And in these cases, for exothermic reactions, the lower the Delta E(P -> TS2) is, the broader the STR is and the later the STS appears.

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