The thermochemistry of group 15 tetrachloride anions

Walker, Barry W.; Check, Catherine E.; Lobring, Kim C.; Pommerening, Cynthia Ann; Sunderlin, Lee S.

doi:10.1016/s1044-0305(02)00369-0

Cited by 12 publications

(18 citation statements)

References 53 publications

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“…The bond strengths in the group 15 tetrachloride anions are also much stronger for heavier central elements: PCl 4 -, AsCl 4 -, and SbCl 4are bound by 90 ( 7, 115 ( 7, and 161 ( 8 kJ mol -1 , respectively. 64 However, the Pauling electronegativities of P, As, and Sb (2.19, 2.18, and 2.05, respectively) are very similar, as are the values for S and Se (2.58 and 2.55; the Te value is 2.10). Thus, central atom electronegativity is not well correlated with group 15 or 16 hypervalent bond strengths.…”

Section: Defined the Covalency Ratio χmentioning

confidence: 90%

Bond Strengths in ChCl₃^-and ChOCl₃^-(Ch = S, Se, Te): Experiment and Theory

et al. 2003

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The strengths of the SeCl2−Cl-, SeOCl2−Cl-, SeBr2−Br-, and TeCl2−Cl- bonds have been measured to be 133 ± 9, 150 ± 10, 110 ± 6, and 170 ± 7 kJ mol-1, respectively, by determining thresholds for collision-induced dissociation in a flowing afterglow-tandem mass spectrometer. These values are stronger than the previously measured D(SCl2−Cl-) and D(SOCl2−Cl-), both 85 ± 8 kJ mol-1. Bond energies and other properties for these molecules and TeOCl3 - have also been computed by several high-level computational techniques, including B3LYP/aug-cc-pVTZ. There is excellent agreement between the experimental and computational energetics for SeCl3 -, SeOCl3 -, and TeCl3 -. The bond strengths increase in the order S < Se < Te.

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Section: Defined the Covalency Ratio χmentioning

confidence: 90%

Bond Strengths in ChCl₃^-and ChOCl₃^-(Ch = S, Se, Te): Experiment and Theory

et al. 2003

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“…While this could conceivably be due to the experimental uncertainties, it is probably a systematic effect: previous cases have been noted where the heavier, more polarizable collision gas Xe (which is more likely to form a complex with the CID target and efficiently transfer energy from translational into internal degrees of freedom) gives lower thresholds that are more consistent with known thermochemistry (14, 38, 39). This is not always the case (40); systems with strong bonds and low densities of states (few atoms and high vibrational frequencies) are more likely to show this collision gas effect. Since the SO 3 Cl -and SO 3 Br -systems appear to show a moderate threshold shift of this type, SO 3 F -is likely to have a greater one.…”

Section: Experimental Bond Dissociation Energiesmentioning

confidence: 99%

The bond dissociation energies of SO₃X (X = F, Cl, Br, and I)

Hao¹,

Gilbert²,

Sunderlin³

2005

Can. J. Chem.

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The gas-phase strengths of the SO 3 -X -bonds (X = Cl, Br, and I) have been determined to be 222 ± 13, 179 ± 11, and 161 ± 9 kJ/mol, respectively, by measuring thresholds for collision-induced dissociation in a flowing afterglow-tandem mass spectrometer. An upper limit of D(SO 3 -F -) ≤ 488 ± 19 kJ/mol was also determined. The periodic trends in the halide affinities of SO 3 closely parallel those for SO 2 and other Lewis acids. Bond strengths computed using the B3LYP, MP2, QCISD(T), and other models with several basis sets are generally lower than experiment.Résumé : Utilisant un spectromètre de masse en tandem à écoulement postluminescence, on a mesuré les seuils de dissociation induite par une collision et on en déduit que les forces, en phase gazeuse, des liaisons SO 3 -X -(X = Cl, Br et I) sont respectivement de 222 ± 13, 179 ± 11 et 161 ± 9 kJ/mol. On a aussi déterminé que la limite supérieure de D(SO 3 -F -) est ≤ 488 ± 19 kJ/mol. Les tendances périodiques dans les affinités des halogénures pour le SO 3 sont parallèles à celles pour le SO 2 et pour d'autres acides de Lewis. Les forces des liaisons calculées par les méthodes B3LYP, MP2, QCISD(T) et d'autres modèles en utilisant plusieurs ensembles de bases sont généralement inférieures aux valeurs expérimentales.

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“…Optimized geometrical parameters and computed harmonic vibrational frequencies of AsX and AsX 3 species, where X = H, F or Cl, obtained in the present study are given in Tables 2 and 3 respectively. Available experimental values [38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] are included in these tables for comparison. (For AsX 2 species, see also our previous works).…”

Section: Results and Discussion Iiia Geometrical Parameters And Vibra...mentioning

confidence: 99%

The enthalpies of formation of AsXn molecules, where X = H, F or Cl, and n = 1, 2 or 3, by RCCSD(T) and UCCSD(T)-F12x calculations

Mok

Lee

Chau

et al. 2011

Phys. Chem. Chem. Phys.

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RCCSD(T) and UCCSD(T)-F12x calculations were performed on AsX(n) molecules, where X = H, F or Cl, and n = 1, 2 or 3, and related species, in order to evaluate their enthalpies of formation (ΔH(f)(Ø)). The recommended ΔH(f)(Ø) values obtained from the present investigation are AsH, 57.7(2); AsF, -7.9(3); AsCl, 27.2(4); AsH(2), 39.8(4); AsF(2), -96.6(9); AsCl(2), -17.8(10); AsH(3), 17.1(4); AsF(3)-196.0(5) and AsCl(3), -59.1(27) kcal mole(-1). These values are anchored only on one thermodynamic quantity, namely, ΔH(f)(Ø)(As) (= 70.3 kcal mole(-1)). In the calculations, the fully-relativistic small-core effective core potential (ECP10MDF) was used for As. Contributions from outer core correlation of As 3d(10) electrons were computed explicitly in both RCCSD(T) and UCCSD(T)-F12 calculations with additional tight basis functions designed for As 3d(10) electrons. Basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality were used in RCCSD(T) calculations and computed relative electronic energies were extrapolated to the complete basis set (CBS) limit. For the simplified, explicitly correlated UCCSD(T)-F12x calculations, basis sets of up to quadruple-zeta (QZ) quality were employed. Based on the RCCSD(T)/CBS benchmark values, the reliability of available theoretical and experimental values have been assessed.

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The thermochemistry of group 15 tetrachloride anions

Cited by 12 publications

References 53 publications

Bond Strengths in ChCl₃^-and ChOCl₃^-(Ch = S, Se, Te): Experiment and Theory

Bond Strengths in ChCl₃^-and ChOCl₃^-(Ch = S, Se, Te): Experiment and Theory

The bond dissociation energies of SO₃X (X = F, Cl, Br, and I)

The enthalpies of formation of AsXn molecules, where X = H, F or Cl, and n = 1, 2 or 3, by RCCSD(T) and UCCSD(T)-F12x calculations

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The thermochemistry of group 15 tetrachloride anions

Cited by 12 publications

References 53 publications

Bond Strengths in ChCl3-and ChOCl3-(Ch = S, Se, Te): Experiment and Theory

Bond Strengths in ChCl3-and ChOCl3-(Ch = S, Se, Te): Experiment and Theory

The bond dissociation energies of SO3X (X = F, Cl, Br, and I)

The enthalpies of formation of AsXn molecules, where X = H, F or Cl, and n = 1, 2 or 3, by RCCSD(T) and UCCSD(T)-F12x calculations

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Bond Strengths in ChCl₃^-and ChOCl₃^-(Ch = S, Se, Te): Experiment and Theory

Bond Strengths in ChCl₃^-and ChOCl₃^-(Ch = S, Se, Te): Experiment and Theory

The bond dissociation energies of SO₃X (X = F, Cl, Br, and I)