Anomalous isotopic effect on vibrational properties of HXeOH

Khriachtchev, Leonid; Lundell, Jan; Pettersson, Mika; Tanskanen, Hanna; Räsänen, Markku

doi:10.1063/1.1459703

Cited by 24 publications

(14 citation statements)

References 18 publications

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“…The anharmonic computational approach has been previously applied for other HNgY molecules as a compromise between computational task and accuracy. 44,45 The computations of the radical species were performed at the B3LYP/aug-cc-pVDZ level of theory in order to assess if such open-shell species are stable and thereafter to estimate the effect of the 15 N isotopic substitution. In principle, singlereference wave function methods such as MP2 seem to be unsuitable for these species, and therefore we have followed the path employing density functional theory for the open-shell species.…”

Section: Computationsmentioning

confidence: 99%

Insertion of Noble Gas Atoms into Cyanoacetylene: An ab Initio and Matrix Isolation Study

et al. 2006

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A computational and experimental matrix isolation study of insertion of noble gas atoms into cyanoacetylene (HCCCN) is presented. Twelve novel noble gas insertion compounds are found to be kinetically stable at the MP2 level of theory, including four molecules with argon. The first group of the computationally studied molecules belongs to noble gas hydrides (HNgCCCN and HNgCCNC), and we found their stability for Ng = Ar, Kr, and Xe. The HNgCCCN compounds with Kr and Xe have similar stability to that of previously reported HKrCN and HXeCN. The HArCCCN molecule seems to have a weaker H-Ar bond than in the previously identified HArF molecule. The HNgCCNC molecules are less stable than the HNgCCCN isomers for all noble gas atoms. The second group of the computational insertion compounds, HCCNgCN and HCCNgNC, are of a different type, and they also are kinetically stable for Ng = Ar, Kr, and Xe. Our photolysis and annealing experiments with low-temperature cyanoacetylene/Ng (Ng = Ar, Kr, and Xe) matrixes evidence the formation of two noble gas hydrides for Ng = Kr and Xe, with the strongest IR absorption bands at 1492.1 and 1624.5 cm(-1), and two additional absorption modes for each species are found. The computational spectra of HKrCCCN and HXeCCCN fit most closely the experimental data, which is the basis for our assignment. The obtained species absorb at quite similar frequencies as the known HKrCN and HXeCN molecules, which is in agreement with the theoretical predictions. No strong candidates for an Ar compound are observed in the IR absorption spectra. As an important side product of this work, the data obtained in long-term decay of KrHKr+ cations suggest a tentative assignment for the CCCN radical.

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Section: Computationsmentioning

confidence: 99%

Insertion of Noble Gas Atoms into Cyanoacetylene: An ab Initio and Matrix Isolation Study

et al. 2006

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“…We have recently found experimentally similar oxygen-isotope shifts for HXeOH and HXeOD molecules and described the effect theoretically in terms of anharmonic coupling between the normal modes. 16 The low sensitivity of our apparatus in the far-IR spectral range (<400 cm -1 ) did not allow us to detect the Xe-O stretching vibration that should be more sensitive to oxygen isotope substitution.…”

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confidence: 97%

A Neutral Xenon-Containing Radical, HXeO

et al. 2003

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We report an open-shell species containing xenon, HXeO ((2)Sigma), prepared by UV photolysis of H(2)O/Xe or N(2)O/HBr/Xe solid mixtures at 7 K and subsequent thermal mobilization of oxygen atoms at >/=30 K. The H-Xe stretching absorption of HXeO in solid Xe is at 1466.1 cm(-1), and it shifts to 1070.3 cm(-1) upon deuteration. The extensive ab initio calculations indicate that HXeO is intrinsically stable, owing to significant ionic and covalent contributions to its bonding. The formation of HXeO ((2)Sigma) radicals in these experiments suggests extensive stabilization and thermal mobility of singlet ((1)D) oxygen atoms in solid Xe and holds promises for the stability of the HKrO and HArO species.

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“…However, there is experimental and theoretical evidence for important anharmonic effects for HRgY molecules [6,[16][17][18]. The anharmonic MP2 vibrational frequencies of the HKrCl isotopologues are shown in Table. The H-Kr stretching (n 3 ) is predicted at 1691.0 cm -1 , 250 cm -1 below the corresponding harmonic value.…”

Section: Computational Results and Discussionmentioning

confidence: 99%

Kr–Cl stretching vibration of HKrCl: Matrix-isolation and anharmonic ab initio study

Lignell

Lundell

Pettersson

et al. 2003

Low Temperature Physics

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The Kr–Cl stretching vibration of HKrCl molecule is studied. The absorption shows Cl35 and Cl37 isotopic splitting due to natural abundance of the Cl isotopes. The observed Kr–Cl stretching vibrations of the HKrCl are at 253.1 (35Cl) and 248.3 cm−1 (37Cl). Experimentally, deuteration of the HKrCl does not cause a shift of the Kr–Cl stretching frequency. In addition to the Kr–Cl stretching mode, the bending mode of DKrCl is observed at 397.7 cm−1. The vibrational analysis suggests that the Kr–Cl bond shows some covalent character in addition to the ionic. Anharmonic ab initio calculations are employed to verify the vibrational properties of various isotopologues of HKrCl.

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Anomalous isotopic effect on vibrational properties of HXeOH

Cited by 24 publications

References 18 publications

Insertion of Noble Gas Atoms into Cyanoacetylene: An ab Initio and Matrix Isolation Study

Insertion of Noble Gas Atoms into Cyanoacetylene: An ab Initio and Matrix Isolation Study

A Neutral Xenon-Containing Radical, HXeO

Kr–Cl stretching vibration of HKrCl: Matrix-isolation and anharmonic ab initio study

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