The Interaction of Water and Dibromine in the Gas Phase: An Investigation of the Complex H2O⋅⋅⋅Br2 by Rotational Spectroscopy and Ab Initio Calculations

Legon, A. C.; Thumwood, J. M. A.; Waclawik, Eric R.

doi:10.1002/1521-3765(20020215)8:4<940::aid-chem940>3.0.co;2-h

Cited by 44 publications

(47 citation statements)

References 43 publications

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“…Other molecules H 2 O⋯HX were studied in the vibrational ground state by pulsed‐jet, Fourier‐transform microwave spectroscopy, but the equilibrium geometry was deduced by various observations to be again pyramidal at O, with a low barrier to inversion, as confirmed by ab initio calculations. A similar conclusion obtains for several halogen‐bonded complexes H 2 O⋯XY (XY is a homo‐ or hetero‐nuclear di‐halogen molecule). Equilibrium values ϕ e were estimated to lie in the range 35‐55° from the rotational constants of each H 2 O⋯HX and H 2 O⋯XY investigated.…”

Section: Introductionsupporting

confidence: 78%

Nonbonding pairs in cyclic thioethers: Electrostatic modeling and ab initio calculations for complexes of 2,5‐dihydrothiophene, thietane, and thiirane with hydrogen fluoride

Hill

Legon²

2018

Int J of Quantum Chemistry

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Electrostatic potential energies V(ϕ) of a non‐perturbing, protonic charge at fixed distances r from the S atom in three cyclic thioethers were examined as functions of the angles ϕ made by the r‐vector with the C2 axis (thiirane and 2,5‐dihydrothiophene) or the local C2 axis (thietane). The electrostatic PE VHF(ϕ) of HF (HF modelled as an extended electric dipole) was also calculated and the results compared with geometries of the thioether⋯HF complexes calculated at the CCSD(T)‐F12c/cc‐pVTZ‐F12 level. The latter reveal angular deviations θ ∼10‐20° of the S⋯HF nuclei from collinearity in directions suggesting secondary interactions of F with H atom(s) of the rings. Angles ϕ made by the S⋯H hydrogen bond with the C2 (or local C2) axes in the complexes are systematically larger (∼4‐9°) than indicated by the VHF(ϕ) functions. Minima in the simple V(ϕ) versus ϕ functions occur at values smaller (∼5‐10°) than those in the VHF(ϕ) curves.

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Section: Introductionsupporting

confidence: 78%

Nonbonding pairs in cyclic thioethers: Electrostatic modeling and ab initio calculations for complexes of 2,5‐dihydrothiophene, thietane, and thiirane with hydrogen fluoride

Hill

Legon²

2018

Int J of Quantum Chemistry

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“…Single point energies of the optimized systems were further calculated at the MP2/aug-cc-pVDZ level. This level of theory was thought to be adequate for reasonably weak nonbonding interactions, and was successfully used in theoretical studies of X-bonded complexes formed between halogenated compounds and H 2 O or H 2 S (Legon and Thumwood, 2001;Legon et al, 2002). The interaction energies (DE) of complexes were obtained under the supermolecule approach (Chesnut and Moseley, 1969); this method considers the difference between the total energy of the complex and the sum total energies of isolated monomers, viz., DE = E complex À (E monomer1 + E monomer2 ).…”

Section: Quantum Mechanical Calculationmentioning

confidence: 99%

Halogen–water–hydrogen bridges in biomolecules

Zhou

Zou

et al. 2010

Journal of Structural Biology

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“…In analogy with H 2 O-Cl 2 22 and H 2 O-Br 2 dimers, 23 the ground state is expected to be stabilized by a strong O-I bond between the nearest neighbor water molecule and the iodine molecule. The H 2 O-Cl 2 and H 2 O-Br 2 well depths are about 2 and 3 kcal/ mol, respectively; 24 if H 2 O-I 2 follows this trend, the O-I bond should be even stronger.…”

Section: Uv-vis Spectroscopy As Illustrated Inmentioning

confidence: 99%

Spectroscopic Signatures of Halogens in Clathrate Hydrate Cages. 2. Iodine

et al. 2007

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UV-vis and Raman spectroscopy were used to study iodine molecules trapped in sII clathrate hydrate structures stabilized by THF, CH 2 Cl 2 , or CHCl 3 . The spectra show that the environment for iodine inside the water cage is significantly less perturbed than either in aqueous solution or in amorphous water-ice. The resonance Raman progression of I 2 in THF clathrate hydrate can be observed up to V ) 6 when excited at 532 nm. The extracted vibrational frequency ω e ) 214 ( 1 cm -1 is the same as that of the free molecule to within experimental error. At the same time, the UV-vis absorption spectrum of I 2 in the sII hydrate exhibits a relatively large, 1440 cm -1 , blue-shift. This is mainly ascribed to the differential solvation of the I 2 electronic states. We conclude that iodine in sII hydrate resides in a 5 12 6 4 cavity, in which the ground-state I 2 potential is not significantly perturbed by the hydrate lattice. In contrast, in water and in ice, the valence absorption band of I 2 is dramatically broadened and blue-shifted by 3000 cm, and the resonance Raman scattering is effectively quenched. These observations are shown to be consistent with a strong interaction between water molecule and iodine through the lone pair of electrons on water as in the case of bromine in the same media. The results presented here, and the stability of other halogen hydrates, were used to test the predictions of simple models and force-field calculations of the host cage-guest association energy.

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The Interaction of Water and Dibromine in the Gas Phase: An Investigation of the Complex H2O⋅⋅⋅Br2 by Rotational Spectroscopy and Ab Initio Calculations

Cited by 44 publications

References 43 publications

Nonbonding pairs in cyclic thioethers: Electrostatic modeling and ab initio calculations for complexes of 2,5‐dihydrothiophene, thietane, and thiirane with hydrogen fluoride

Nonbonding pairs in cyclic thioethers: Electrostatic modeling and ab initio calculations for complexes of 2,5‐dihydrothiophene, thietane, and thiirane with hydrogen fluoride

Halogen–water–hydrogen bridges in biomolecules

Spectroscopic Signatures of Halogens in Clathrate Hydrate Cages. 2. Iodine

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