Interaction of rare-gas-containing molecules with nitrogen: Matrix-isolation and <i>ab initio</i> study of HArF⋯N2, HKrF⋯N2, and HKrCl⋯N2 complexes

Lignell, Antti; Khriachtchev, Leonid; Pettersson, Mika; Räsänen, Markku

doi:10.1063/1.1575198

Cited by 88 publications

(54 citation statements)

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“…4,[22][23][24][25] The R(0) branch produces the strongest bands at 2900, 2887.5, 2872.5, and 2858 cm −1 in Ne, Ar, Kr, and Xe matrices, respectively, red-shifted from the gas-phase value of 2905.7 cm −1 (for the main isotope 35 Cl). The H 37 Cl absorptions are ∼2 cm −1 lower in energy.…”

Section: B Experimental Resultsmentioning

confidence: 99%

Matrix effect on vibrational frequencies: Experiments and simulations for HCl and HNgCl (Ng = Kr and Xe)

Kalinowski

Gerber

Räsänen

et al. 2014

The Journal of Chemical Physics

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We study the environmental effect on molecules embedded in noble-gas (Ng) matrices. The experimental data on HXeCl and HKrCl in Ng matrices is enriched. As a result, the H−Xe stretching bands of HXeCl are now known in four Ng matrices (Ne, Ar, Kr, and Xe), and HKrCl is now known in Ar and Kr matrices. The order of the H−Xe stretching frequencies of HXeCl in different matrices is ν(Ne) < ν(Xe) < ν(Kr) < ν(Ar), which is a non-monotonous function of the dielectric constant, in contrast to the "classical" order observed for HCl: ν(Xe) < ν(Kr) < ν(Ar) < ν(Ne). The order of the H−Kr stretching frequencies of HKrCl is consistently ν(Kr) < ν(Ar). These matrix effects are analyzed theoretically by using a number of quantum chemical methods. The calculations on these molecules (HCl, HXeCl, and HKrCl) embedded in single Ng layer cages lead to very satisfactory results with respect to the relative matrix shifts in the case of the MP4(SDQ) method whereas the B3LYP-D and MP2 methods fail to fully reproduce these experimental results. The obtained order of frequencies is discussed in terms of the size available for the Ng hydrides in the cages, probably leading to different stresses on the embedded molecule. Taking into account vibrational anharmonicity produces a good agreement of the MP4(SDQ) frequencies of HCl and HXeCl with the experimental values in different matrices. This work also highlights a number of open questions in the field.

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Section: B Experimental Resultsmentioning

confidence: 99%

Matrix effect on vibrational frequencies: Experiments and simulations for HCl and HNgCl (Ng = Kr and Xe)

Kalinowski

Gerber

Räsänen

et al. 2014

The Journal of Chemical Physics

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“…[45] A hydrogen bond A···H À B is in fact normally accompanied by elongation of the H À B bond and a redshift of its stretching frequency. Numerous subsequent experiments and calculations confirmed, however, that, apart from a few exceptions, [46] the contraction of the HÀNg bond and the blueshift of the corresponding frequency must be viewed as a normal effect for both hydrogen-and Y-cooordinated complexes of HNgY.…”

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confidence: 99%

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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“…. HKrX species comes from Fourier-transform infrared (FTIR) spectroscopy performed in a solid Kr matrix at 7.5 K, 28 while the N 2 . .…”

Section: Discussionmentioning

confidence: 99%

A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N₂

McDowell

2007

J Comput Chem

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Bond length changes, harmonic vibrational frequency shifts, and changes in the proton magnetic shielding of HX and HKrX (X = F, Cl) on complexation with N2 to form the linear red-shifted N2 ... HX and linear blue-shifted N2 ... HKrX complexes were determined by ab initio computations, with and without counterpoise correction, at the SCF and MP2(full) levels of theory using a 6-311++G(2d,2p) basis set. The MP2 computations agree with predictions from a perturbation theory model involving the first and second derivatives of the interaction energy with respect to displacement of the H--X and H--Kr bond lengths from their equilibrium values in the isolated monomers. The theoretical results agree qualitatively with the experimentally observed frequency shifts, with near quantitative agreement for N2 ... HKrCl. The characteristic downfield shift of the isotropic proton magnetic resonance in the red-shifted complexes was obtained, but for the blue-shifted complexes, the proton NMR shifts to higher fields.

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Interaction of rare-gas-containing molecules with nitrogen: Matrix-isolation and ab initio study of HArF⋯N2, HKrF⋯N2, and HKrCl⋯N2 complexes

Cited by 88 publications

References 42 publications

Matrix effect on vibrational frequencies: Experiments and simulations for HCl and HNgCl (Ng = Kr and Xe)

Matrix effect on vibrational frequencies: Experiments and simulations for HCl and HNgCl (Ng = Kr and Xe)

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

A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N₂

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Interaction of rare-gas-containing molecules with nitrogen: Matrix-isolation and ab initio study of HArF⋯N2, HKrF⋯N2, and HKrCl⋯N2 complexes

Cited by 88 publications

References 42 publications

Matrix effect on vibrational frequencies: Experiments and simulations for HCl and HNgCl (Ng = Kr and Xe)

Matrix effect on vibrational frequencies: Experiments and simulations for HCl and HNgCl (Ng = Kr and Xe)

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

A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N2

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A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N₂