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

Kalinowski, Jarosław; Gerber, R. Benny; Räsänen, Markku; Lignell, Antti; Khriachtchev, Leonid

doi:10.1063/1.4866913

Cited by 22 publications

(28 citation statements)

References 55 publications

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“…Evidently, the details of interactions between the embedded molecule and the matrix atoms have changed. Thus, the order of the H-Xe stretching frequencies observed previously for HXeCl, HXeBr, and HXeCCH (ν(Xe) < ν(Kr) < ν(Ar)) 4,6,8,9 is not common for noble-gas hydrides.…”

Section: Concluding Discussionmentioning

confidence: 86%

“…In addition, the calculations predict for HXeI stronger shifts between Xe and other matrices than for HXeCl, 12 in agreement with experiment. 4,9 For HXeH, the ⟨100⟩ (single substitution) site is lower in energy only in Kr and Xe matrices. In an Ar matrix, the ⟨110⟩ (double substitution) site is slightly more preferable.…”

Section: Concluding Discussionmentioning

confidence: 99%

“…Annealing at about 20 K mobilizes the H atoms in an Ar matrix, which should lead to the reaction H + Xe···I → HXeI, similarly to the preparation of other noble-gas hydrides in Ar matrices. 6,8,9 In the spectrum of the photolyzed and annealed HI/Xe/Ar matrices (spectra A and C in Figure 3), two bands appear at 1238.0 and 1203.2 cm −1 . The intensities of these bands increase with the Xe concentration and the band shape also slightly changes with the Xe concentration.…”

Section: Hxei and Hxeh In An Ar Matrixmentioning

confidence: 99%

“…11 Kalinowski et al have performed MP4(SDQ) calculations of HXeCl in noble-gas clusters, and the obtained order of the H-Xe stretching frequencies ν(Ne) < ν(Xe) < ν(Kr) < ν(Ar) is in agreement with the experiment. 9 Kalinowski et al have suggested that the reason for the frequency order ν(Xe) < ν(Kr) < ν(Ar) is in different stress states of the molecules in the cages due to the different cage sizes. The H-Xe stretching frequencies of HXeCl in all matrix environments are surprisingly found to be red-shifted from the value obtained in vacuum.…”

Section: Introductionmentioning

confidence: 99%

“…1 However, in some studies, the HNgY molecules were prepared in "foreign" matrices, of a different material Ng ′ (see Table I). [4][5][6][7][8][9] It is reasonable to assume that the H-Ng stretching frequency increases with the strength of the interaction of HNgY with the environment. From this point of view, the relatively high frequencies of this mode observed in N 2 and CO 2 matrices are expectable due to the dipole-quadrupole interactions between HNgY and matrix molecules.…”

Section: Introductionmentioning

confidence: 99%

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HXeI and HXeH in Ar, Kr, and Xe matrices: Experiment and simulation

Zhu

Niimi

Taketsugu

et al. 2015

The Journal of Chemical Physics

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Experimental and theoretical studies of HXeI and HXeH molecules in Ar, Kr, and Xe matrices are presented. HXeI exhibits the H–Xe stretching bands at 1238.0 and 1239.0 cm−1 in Ar and Kr matrices, respectively, that are blue-shifted from the HXeI band observed in a Xe matrix (1193 cm−1) by 45 and 46 cm−1. These shifts are larger than those observed previously for HXeCl (27 and 16 cm−1) and HXeBr (37 and 23 cm−1); thus, the matrix effect is stronger for less stable molecules. The results for HXeI are qualitatively different from all previous results on noble-gas hydrides with respect to the frequency order between Ar and Kr matrices. For previously studied HXeCl, HXeBr, and HXeCCH, the H–Xe stretching frequency is reliably (by >10 cm−1) higher in an Ar matrix than in a Kr matrix. In contrast, the H–Xe stretching frequency of HXeI in an Ar matrix is slightly lower than that in a Kr matrix. HXeH absorbs in Ar and Kr matrices at 1203.2 and 1192.1 cm−1 (the stronger band for a Kr matrix), respectively. These bands are blue-shifted from the stronger band of HXeH in a Xe matrix (1166 cm−1) by 37 and 26 cm−1, and this frequency order is the same as observed for HXeCl, HXeBr, and HXeCCH but different from HXeI. The present hybrid quantum-classical simulations successfully describe the main experimental findings. For HXeI in the 〈110〉 (double substitution) site, the order of the H–Xe stretching frequencies (ν(Xe) < ν(Ar) < ν(Kr)) is in accord with the experimental observations, and also the frequency shifts in Ar and Kr matrices from a Xe matrix are well predicted (30 and 34 cm−1). Both in the theory and experiment, the order of the H–Xe stretching frequencies differs from the case of HXeCl, which suggests the adequate theoretical description of the matrix effect. For HXeH in the 〈100〉 (single substitution) site, the order of the frequencies is ν(Xe) < ν(Kr) < ν(Ar), which also agrees with the experiments. The calculated frequency shifts for HXeH in Ar and Kr matrices with respect to a Xe matrix (36 and 23 cm−1) are in a good agreement with the experiments. The present calculations predict an increase of the H–Xe stretching frequencies in the noble-gas matrices with respect to vacuum.

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Section: Concluding Discussionmentioning

confidence: 86%

Section: Concluding Discussionmentioning

confidence: 99%

Section: Hxei and Hxeh In An Ar Matrixmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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HXeI and HXeH in Ar, Kr, and Xe matrices: Experiment and simulation

Zhu

Niimi

Taketsugu

et al. 2015

The Journal of Chemical Physics

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Prediction of a Neutral Noble Gas Compound in the Triplet State

Manna

Ghosh

Ghanty

2015

Chemistry A European J

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Discovery of the HArF molecule associated with H-Ar covalent bonding [Nature, 2000, 406, 874-876] has revolutionized the field of noble gas chemistry. In general, this class of noble gas compound involving conventional chemical bonds exists as closed-shell species in a singlet electronic state. For the first time, in a bid to predict neutral noble gas chemical compounds in their triplet electronic state, we have carried out a systematic investigation of xenon inserted FN and FP species by using quantum chemical calculations with density functional theory and various post-Hartree-Fock-based correlated methods, including the multireference configuration interaction technique. The FXeP and FXeN species are predicted to be stable by all the computational methods employed in the present work, such as density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2), coupled-cluster theory (CCSD(T)), and multireference configuration interaction (MRCI). For the purpose of comparison we have also included the Kr-inserted compounds of FN and FP species. Geometrical parameters, dissociation energies, transition-state barrier heights, atomic charge distributions, vibrational frequency data, and atoms-in-molecules properties clearly indicate that it is possible to experimentally realize the most stable state of FXeP and FXeN molecules, which is triplet in nature, through the matrix isolation technique under cryogenic conditions.

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