Combining theory with experiment: Assessment of the thermochemistry of SF{sub n}, SF{sub n}{sup +}, and SF{sub n}{sup -}, n=1-6

Journal Article · Wed Sep 27 00:00:00 EDT 1995 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja00143a016· OSTI ID:121602

Cheung, Y S; Chen, Y J; Ng, C Y ^[1]; Chiu, S W ^[2]; Li, W K ^[3]

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1. Ames Lab., IA (United States)
2. Univ. of Illinois, Urbana, IL (United States)
3. Chinese Univ. of Hong Kong, Shatin (Hong Kong)

The comparison of the experimental thermochemical data and G2 or [G2(MP2)] predictions for SF{sub n}, SF{sub n}{sup +}, and SF{sub n} {sup -} (n = 1-6) allows us to recommend a self-consistent set of experimental {Delta}{sub f}H{degree}{sub 0}, IE, EA, D{degree}{sub 0} values for these systems. This work shows that for reliable determinations of the thermochemical data for a complex system such as SF{sub n}, SF{sub n} {sup +}, and SF{sub n}{sup -} (n = 1-6), it is necessary to combine experimental measurements made using different techniques and theoretical predictions calculated using a sufficiently accurate theoretical procedure. The comparison of experimental and theoretical results in this study further confirms that G2 and G2(MP2) procedures are reliable theoretical methods for providing energetic predictions accurate to 4-5 kcal/mol for complex sulfur-containing molecular species. The theoretical equilibrium structures obtained for SF{sub n}, SF{sub n}{sup +}, and SF{sub n}{sup -} (n = 1-6) have been rationalized using the VSEPR theory. Furthermore, we have provided an explanation to account for the observed alternating patterns in IE, EA, and D{degree}{sub 0} values for SF{sub n}, SF{sub n}{sup +}, and SF{sub n}{sup -} (n = 1-6). Alternating patterns in IE, EA, and D{degree}{sub 0} values are expected for other similar hypervalent species. 60 refs., 2 figs., 4 tabs.

• Sponsoring Organization: USDOE
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 121602
• Journal Information: Journal of the American Chemical Society, Vol. 117, Issue 38; Other Information: PBD: 27 Sep 1995
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
99 MATHEMATICS
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DISSOCIATION ENERGY
MOLECULAR MODELS
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