UNSPECIFIED (2004) A computational study of SbnF(5n) (n=1-4) - Implications for the fluoride ion affinity of nSbF(5). In: International Conference on Fluorine Chemistry, Kyoto, JAPAN, MAY 09-11, 2004. Published in: JOURNAL OF FLUORINE CHEMISTRY, 125 (11). pp. 1585-1592.

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Abstract

This contributions shows with a series of ab initio MP2 and DFT (BP86 and B3-LYP) computations with large basis sets up to cc-pVQZ quality that the literature value of the standard enthalpy of depolymerization of 1/4 Sb4F20(g) to give SbF5(g) (+18.5 kJ mol(-1)) [J. Fawcett, J.H. Holloway, R.D. Peacock, D.R. Russell, J. Fluorine Chem. 20 (1982) 9] is by about 50 kJ mol(-1) in error and that the correct value of Delta(r)Hdegrees(depoly). (1/4 Sb4F20(g)) is +68 +/- 10 kJ mol(-1). We assign Delta(r)Hdegrees(depoly), Delta(r)Hdegrees, Delta(r)Gdegrees and Delta(r)Gdegrees values for SbnF5n with n = 2-4 and compare the results to available experimental gas phase data. Especially the MP2/TZVPP values obtained in an indirect procedure that rely on isodesmic reactions or the highly accurate compound methods G2 and CBS-Q are in excellent agreement with the experimental data, and reproduce also the fine experimental details at temperatures of 423 and 498 K. With these data and the additional calculation of [SbnF5n+1](-) (n = 1-4), we then assessed the fluoride ion affinities (FIAs) of SbnF5n(g), nSbF(5(g)), nSbF(5(l)) and the standard enthalpies of formation of SbnF5n(g) and [SbnF5n+1]((g))(-): FIA(SbnF5n(g)) = 514 (n = 1), 559 (n = 2), 572 (n = 3) and 580 (n = 4) kJ mol(-1); FIA(nSbF(5(g))) = 667 (n = 2), 767 (n = 3) and 855 (n = 4) kJ mol(-1); FIA(nSbF(5(l))) = 434 (n = 1), 506 (n = 2), 528 (n = 3) and 534 (n = 4) kJ mol(-1). Error bars are approximately +/-10 kJ mol(-1). Also the related Gibbs energies were derived. Delta(f)Hdegrees([SbnF5n+1]((g))(-)) = -2064 +/- 18 (n = 1), -3516 +/- 25 (n = 2), -4919 +/- 31 (n = 3) and -6305 +/- 36 (n = 4) kJ mol(-1). (C) 2004 Elsevier B.V. All rights reserved.

Item Type:	Conference Item (UNSPECIFIED)
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	JOURNAL OF FLUORINE CHEMISTRY
Publisher:	ELSEVIER SCIENCE SA
ISSN:	0022-1139
Date:	November 2004
Volume:	125
Number:	11
Number of Pages:	8
Page Range:	pp. 1585-1592
Identification Number:	10.1016/j.jfluchem.2004.09.016
Publication Status:	Published
Title of Event:	International Conference on Fluorine Chemistry
Location of Event:	Kyoto, JAPAN
Date(s) of Event:	MAY 09-11, 2004
URI:	http://wrap.warwick.ac.uk/id/eprint/7557

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