Matrix-Isolation and Ab Initio Study of the HKrCl···HCl Complex

Corani, Alice; Domanskaya, Alexandra; Khriachtchev, Leonid; Räsänen, Markku; Lignell, Antti

doi:10.1021/jp9044622

Cited by 31 publications

(27 citation statements)

References 29 publications

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“…For example, interaction with nitrogen produces a larger effect on HArF than on HKrF, 8 and interaction with HCl and nitrogen affects the properties of HKrCl more than the properties of HXeCl. 8,10,11,13 The experimental spectroscopic data are consistent with the quantum chemical calculations.…”

Section: -5supporting

confidence: 81%

Matrix-isolation and computational study of the HKrCCH⋯HCCH complex

et al. 2015

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The HKrCCH/HCCH complex is identified in a Kr matrix with the H-Kr stretching bands at 1316.5 and 1305 cm À1. The monomer-to-complex shift of the H-Kr stretching mode is about +60 cm À1 , which is significantly larger than that reported previously for the HXeCCH/HCCH complex in a Xe matrix (about +25 cm À1 ). The HKrCCH/HCCH complex in a Kr matrix is formed at $40 K via the attachment of mobile acetylene molecules to the HKrCCH monomers formed at somewhat lower annealing temperatures upon thermally-induced mobility of H atoms ($30 K). The same mechanism was previously proposed for the formation of the HXeCCH/HCCH complex in a Xe matrix. The assignment of the HKrCCH/HCCH complex is fully supported by the quantum chemical calculations. The experimental shift of the H-Kr stretching mode is comparable with the computational predictions (+46.6, +66.0, and +83.2 cm À1 at the B3LYP, MP2, and CCSD(T) levels of theory, respectively), which are also bigger that the calculated shift in the HXeCCH/HCCH complex. These results confirm that the complexation effect is bigger for less stable noble-gas hydrides.

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Section: -5supporting

confidence: 81%

Matrix-isolation and computational study of the HKrCCH⋯HCCH complex

et al. 2015

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“…[21][22][23][24][25] These molecules are characterized by weak bonding and large dipole moments, which leads to a strong complexation effect on the vibrational properties of these molecules. [26][27][28][29][30] In all HNgY complexes studied experimentally, the H-Ng stretching modes exhibit blue shifts, explained by the enhancement of charge separation in these molecules. 28 The HXeI molecule is one of the least stable noblegas hydrides as judged by the very small dissociation energy a) Present address: Department of Applied Chemistry, National Chiao Tung University, 1001 Ta-Hsueh Road, Hsinchu 30010, Taiwan.…”

Section: Introductionmentioning

confidence: 94%

Experimental and theoretical study of the HXeI⋯HCl and HXeI⋯HCCH complexes

Zhu

Tsuge

Räsänen

et al. 2015

The Journal of Chemical Physics

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The HXeI⋯HCl and HXeI⋯HCCH complexes are studied computationally and experimentally in a Xe matrix. In the experiments, three bands of the HXeI⋯HCl complex and one band of the HXeI⋯HCCH complex in the H-Xe stretching region are observed. The monomer-to-complex shifts are +94, +111, and +155 cm(-1) for the HXeI⋯HCl complex and +49 cm(-1) for the HXeI⋯HCCH complex. The bands of the complexed HCl molecules are also observed with large red shifts from the HCl monomer (-187, -252, and -337 cm(-1)). The ab initio calculations at the CCSD(T)/def2-TZVPPD level of theory predict two stable structures for the HXeI⋯HCl complex with interaction energies of -3.72 and -0.28 kcal mol(-1) and one structure for the HXeI⋯HCCH complex with an interaction energy of -2.67 kcal mol(-1) and the calculated monomer-to-complex shifts are in a good agreement with experiment (in the case of HXeI⋯HCl, for the stronger structure). The HXeI molecules are decomposed by broad-band infrared light; however, the decomposition is much more efficient for the HXeI monomer than for the complexes studied here as well as for the previously studied HXeI⋯HI and HXeI⋯HBr complexes. In fact, the decomposition efficiency decreases as the monomer-to-complex shift of the H-Xe stretching mode increases.

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“…Quite recently, the larger stability of the halogen-coordinated complexes of HNgY (Y = halogen atom) was confirmed by experiment. HKrCl-HCl, [43] HXeCl-HCl, [44] and HXeBr-HBr [44] were in fact observed in cold matrices together with their corresponding hydrogencoordinated structures HX-HNgY. Based also on theoretical calculations, the halogen-coordinated structures were characterized by particularly large blueshifts of the H À Ng bonds.…”

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confidence: 92%

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

Giordani

Antoniotti

Grandinetti

2010

Chemistry A European J

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Ab initio calculations at the MP2 and CCSD(T) levels of theory have disclosed the conceivable existence of fluorine-coordinated complexes of HHeF with alkali-metal ions and molecules M(+) (M(+)=Li(+)-Cs(+)), M(+)-OH(2), M(+)-NH(3) (M(+)=Li(+), Na(+)), and MX (M=Li, Na; X=F, Cl, Br). All these ligands L induce a shortening of the H-He distance and a lengthening of the He-F distance accompanied by consistent blue- and redshifts, respectively, of the H-He and He-F stretching modes. These structural effects are qualitatively similar to those predicted for other investigated complexes of the noble gas hydrides HNgY, but are quantitatively more pronounced. For example, the blueshifts of the H-He stretching mode are exceptionally large, ranging between around 750 and 1000 cm(-1). The interactions of HHeF with the ligands investigated herein also enhance the (HHe)(+)F(-) dipole character and produce large complexation energies of around 20-60 kcal mol(-1). Most of the HHeF-L complexes are indeed so stable that the three-body dissociation of HHeF into H+He+F, exothermic by around 25-30 kcal mol(-1), becomes endothermic. This effect is, however, accompanied by a strong decrease in the H-He-F bending barrier. The complexation energies, DeltaE, and the bending barriers, E*, are, in particular, related by the inverse relationship E*(kcal mol(-1))=6.9exp[-0.041DeltaE(kcal mol(-1))]. Therefore the HHeF-L complexes, which are definitely stable with respect to H+He+F+L (DeltaE approximately 25-30 kcal mol(-1)), are predicted to have bending barriers of only 0.5-2 kcal mol(-1). Overall, our calculations cast doubt on the conceivable stabilization of HHeF by complexation.

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Matrix-Isolation and Ab Initio Study of the HKrCl···HCl Complex

Cited by 31 publications

References 29 publications

Matrix-isolation and computational study of the HKrCCH⋯HCCH complex

Matrix-isolation and computational study of the HKrCCH⋯HCCH complex

Experimental and theoretical study of the HXeI⋯HCl and HXeI⋯HCCH complexes

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

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