Hydrogen Bonding of Hydrazoic Acid in Solid Nitrogen

Pimentel, George C.; Charles, S.W.; Rosengren, K. Johan

doi:10.1063/1.1727175

Cited by 34 publications

(11 citation statements)

References 11 publications

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“…Additional IR-spectra of matrix isolated HN 3 molecules show besides the monomer absorptions a band in the range of the ν 1 at 3171 cm −1 as well as two sharp bands in the range of the ν 2 at 2142 and 2162 cm −1 , respectively, which can be attributed to dimer bands in good agreement with previous results reported by Pimentel et al [74]. These spectra can be interpreted as two HN 3 molecules linked in head-to-tail or head-to-head orientation forming the dimer.…”

Section: Summary Of the Experimental Resultssupporting

confidence: 90%

Adsorption of Hydrogen Azide on the NaCl(100) Single Crystal Surface. Orientational and Translational Ordering of the HN3 Monolayer as Revealed by PIRS, LEED and Spectra Simulation

Heidberg¹,

Hustedt²,

Oppermann³

et al. 2001

Zeitschrift Für Physikalische Chemie

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The adsorption of hydrogen azide HN 3 on NaCl(100) has been studied by means of polarization Fourier transform infrared spectroscopy PIRS and low energy electron diffraction LEED. The well-defined surface was prepared in-situ under UHV by cleaving a single crystal with as few dislocations as possible.Ordered molecular adsorption of HN 3 has been observed. Multiple absorptions of all four molecular vibrations with frequencies between 4000 and 1000 cm −1 , all nondegenerate in the gas, are found at 120 K. In particular, a quartet of strongly polarized sharp absorption lines for the asymmetric stretching vibration ν 2 at 2162.8, 2154.0, 2149.2, and 2138.3 cm −1 is obtained, the line at 2162.8 cm −1 being extremely weak in s-polarization. Saturation of adsorption, indicating the monolayer, is observed both upon dosing HN 3 in the low coverage range, where island growth is inferred, and desorbing HN 3 from multilayers. No domain orientation appears to be preferred. An activation energy of desorption of 43 ± 5 kJ/mol and a pre-exponential factor of 2.6 × 10 14±1.5 s −1 were determined.Isotopic mixture experiments with H 14 N 3 and H 14 N 15 N 14 N reveal that the four absorption lines of the ν 2 vibration are caused first by site splitting due to two energetically inequivalent HN 3 -species and second by Davydov splitting due to a strong correlation field between the dynamic dipoles. There are four molecules per adsorbate unit cell: two different pairs of energetically equivalent but translationally inequivalent molecules. Further, two different pairs of NH hydrogen bonds are observed. Tilt angles and intermolecular angles of the adsorbed molecules were determined. The translational symmetry of the adsorbate was derived by LEED. Simulation of the ν 2 quartet spectrum based on equations of classical electrodynamics was accomplished yielding the angles, lateral distances and dynamic vibrational couplings within the monolayer. Combining all results we propose a monolayer structure of angularly ordered zigzag chains of HN 3 molecules, where two molecules are linked by a hydrogen bond forming a dimer, while the other weaker hydrogen bond ties the dimers together or to a Cl − surface ion. Two HN 3 dimers make up the p(2 × 2) monolayer unit cell of 2D space group pg.

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Section: Summary Of the Experimental Resultssupporting

confidence: 90%

Adsorption of Hydrogen Azide on the NaCl(100) Single Crystal Surface. Orientational and Translational Ordering of the HN3 Monolayer as Revealed by PIRS, LEED and Spectra Simulation

Heidberg¹,

Hustedt²,

Oppermann³

et al. 2001

Zeitschrift Für Physikalische Chemie

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“…The spectrum of the matrix-isolated azide has been reported previously [52][53][54][55][56]. Himmel et al [52] described signals at 3317, 2135, 1263, 1146 and 533 cm −1 as fingerprints of azide.…”

Section: Uv Irradiation Experiments (λ > 235 Nm)mentioning

confidence: 87%

Photochemistry of 1-phenyl-tetrazolone isolated in solid argon

Gómez‐Zavaglia

Reva

Frija

et al. 2006

Journal of Photochemistry and Photobiology A: Chemistry

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The molecular structure, vibrational spectra, tautomerism and photochemistry of the derivative of tetrazole, 1-phenyl-tetrazolone (C 7 H 6 N 4 O; PT) have been studied by FT-IR matrix isolation spectroscopy and DFT/B3LYP/6-311++G(d,p) calculations. Among the five structures in which PT could be expected to exist (two keto tautomers, one mesoionic olate-form and two different conformers of the hydroxyl tautomer), only the most stable species, 1-phenyl-1,4-dihydro-5H-tetrazol-5-one, could be experimentally observed in low temperature argon matrices. Monomers of this tautomer give rise to an IR spectrum that fits nicely the calculated spectrum obtained at the DFT/B3LYP/6-311++G(d,p) level of theory. In situ UV irradiation (λ > 235 nm) of the matrix-isolated PT induces three main photochemical processes, all of them involving cleavage of the tetrazole ring: e.g. (1) molecular nitrogen loss, with production of 1-phenyl-diaziridin-3-one; this compound reacts subsequently to form 1-aza-1,2,4,6cycloheptatetraene and isocyanic acid (eventually, also to form CO plus phenyldiazene); (2) cleavage of the C (5) -N (1) and N (3) -N (4) tetrazole-ring bonds, with production of phenylazide and isocyanic acid, with phenylazide then losing N 2 to yield as final product 1-aza-1,2,4,6-cycloheptatetraene; and (3) cleavage of the N (1) -N (2) and N (4) -C (5) tetrazole-ring bonds, to yield phenylisocyanate and azide. The observed photochemical processes are distinct from the preferred thermal fragmentation channel, where CO is produced together with a weak IR absorbant species.

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“…Identification of this species is complicated by the fact that its most intense band (nNaN C aN K antisymmetric stretching) is expected to lie nearly at the same position as the nNaCaS antisymmetric stretching of methyl isothiocyanate [37] and to have an intrinsic intensity considerably lower than this latter (405 km mol K1 ; DFT(B3LYP)/6-311CCG(d,p) calculated value). However, the spectrum of matrix-isolated azide is well known [37][38][39][40][41] and the analysis of other regions of the spectra reveals that this species is not present in the irradiated matrix. Indeed, matrix-isolated azide was found to be photochemically labile when subjected to UV-irradiation (lO254 nm [37]), giving rise to N 2 and ( 3 S) HN.…”

Section: Uv-irradiation Experiments (Lo 235 Nm)mentioning

confidence: 99%

Molecular structure, vibrational spectra and photochemistry of 5-mercapto-1-methyltetrazole

Gómez‐Zavaglia

Reva

Frija

et al. 2006

Journal of Molecular Structure

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In this work, 5-mercapto-1-methyltetrazole was studied by low temperature matrix-isolation and solid-state infrared spectroscopy, DFT(B3LYP)/6-311CCG(d,p) calculations and photochemical methods. In the low temperature neat solid phase and isolated in an argon matrix, the compound was found to exist in the 1-methyl-1,4-dihydro-5H-tetrazole-5-thione tautomeric form. The infrared spectra of the compound were fully assigned and correlated with structural properties. In situ UV-irradiation (lO235 nm) of the matrix-isolated monomer is shown to induce different photochemical processes, all of them involving cleavage of the tetrazole ring: e.g. (1) molecular nitrogen expulsion, with production of 1-methyl-1H-diazirene-3-thiol, which is produced in two different conformers; (2) ring cleavage leading to production of methyl isothiocyanate and azide; (3) simultaneous elimination of nitrogen and sulphur with production of N-methylcarbodiimide. Following these photoprocesses, subsequent reactions occur, leading to production of methyl diazene, carbon monosulphide and nitrogen hydride. Spectroscopic evidence of the production of the above-mentioned chemical species is provided.

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Hydrogen Bonding of Hydrazoic Acid in Solid Nitrogen

Cited by 34 publications

References 11 publications

Adsorption of Hydrogen Azide on the NaCl(100) Single Crystal Surface. Orientational and Translational Ordering of the HN3 Monolayer as Revealed by PIRS, LEED and Spectra Simulation

Adsorption of Hydrogen Azide on the NaCl(100) Single Crystal Surface. Orientational and Translational Ordering of the HN3 Monolayer as Revealed by PIRS, LEED and Spectra Simulation

Photochemistry of 1-phenyl-tetrazolone isolated in solid argon

Molecular structure, vibrational spectra and photochemistry of 5-mercapto-1-methyltetrazole

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