14333-26-7Relevant articles and documents
Mode specific internal and direct rotational predissociation in HeHF, HeDF, and HeHCl: van der Waals complexes in the weak binding limit
Lovejoy, Christopher M.,Nesbitt, David J.
, p. 5387 - 5407 (1990)
The near-infrared vibration-rotation spectra of the weakly bound complexes HeHF, HeDF, and HeHCl are observed in a slit supersonic expansion.The spectra correspond to simultaneous excitation of vibration and internal rotation of the H(D)X subunit within the complex.The HeHF and HeDF P/R branch transitions show J-dependent excess linewidths, which are attributed to rapid predissociation of the excited states from intramolecular rotation-translation energy transfer.The corresponding P/R branch transitions in HeHCl are not observed despite good S/N on the Q branch, suggesting even more rapid predissociation for the upper state of this complex.The Q branch transitions for all three complexes abruptly terminate at low J, yielding lower limits to the number of bound rotational states and good estimates of the dissociation energies D0 = 7.1 +/- 0.1 cm-1 for HeHF and HeDF, and 10.1 +/- 1.2 cm-1 for HeHCl.In addition to isotropic intermolecular potentials, the HeHF/HeDF data yield considerable information on the potential anisotropy in the region sampled by the bound and quasibound states.The information so obtained is complementary to results from scattering studies and provides sensitive tests for refining trial potential energy surfaces.
Fischer, R. A.,Gertitschke, P. L.,Manz, J.,Schor, H. H. R.
, p. 100 - 108 (1989)
Bartoszek, F. E.,Manos, D. M.,Polanyi, J. C.
, p. 933 - 935 (1978)
Infrared spectra of the very weak H2--HF and O2--HF complexes in solid neon
Hunt, Rodney D.,Andrews, Lester
, p. 3781 - 3786 (1987)
Very weak, hydrogen bonded complexes of molecular hydrogen and oxygen with HF have been prepared by condensing the neon diluted reagents at 4-5 K.Infrared spectra of the H2-- HF complex revealed a νs (HF) mode at 3938 cm-1 and νc(H2) mode at 4155 cm-1 which are red shifted from isolated molecule values in agreement with theoretical predictions.Increasing the HF concentration produced a 1:2 complex, H2-(HF)2.Similar experimental results were obtained for molecular oxygen complexes using HF and DF; the oxygen fundamental in this complex, however, exhibited a 6 cm-1 blue shift.Spectra of these complexes in argon matrices showed that argon is not an effectively inert medium for very weak complexes where interaction with the solid argon environment is competitive with the H2-HF and O2-HF interactions.
Infrared Spectra of Cyanogen Halide Complexes with Hydrogen Fluoride in Solid Argon
Hunt, Rodney D.,Andrews, Lester
, p. 5594 - 5598 (1987)
Cyanogen chloride was condensed at 12 K with HF in excess argon, producing two 1:1 complexes of the form ClHN--HF (1) and HF--ClCN (2).Increasing the HF concentration produced a 1:2 complex, ClCN--(HF)2, while increasing the ClCN concentration produced a 2:1 complex, ClCN--HF--ClCN.The HF submolecule stretching frequency for the major primary 1:1 complex (1) was observed at 3597 cm-1, and a single HF liberational mode appeared at 602 cm-1.These fundamentals are comparable to the HF modes for alkyl cyanide complexes.In sharp contrast, the second 1:1 complex (2), which is similar to the HF--ClF and HF--Cl2 complexes, displayed a HF stretching frequency at 3912 cm-1.Similarresults were obtained for cyanogen bromide and cyanogen iodide complexes with hydrogen fluoride and deuterium fluoride.In addition, the photolysis of hydrogen cyanide and fluorine produced the complex FCN--HF with no evidence for a complex analogous to 2.The HF stretching and liberational modes for this complex were observed at 3662 and 553 cm-1, respectively.Similarly, the reaction between cyanogen and HF formed only the NCCN--HF complex.The HF modes for this complex were observed at 3757 and 460 cm-1, which indicate a weaker interaction than found for the cyanogen halides and HF.
Infrared spectra of HF complexes with methane, silane, and germane
Davis, Steven R.,Andrews, Lester
, p. 3765 - 3772 (1987)
HF complexes with methane, silane, and germane were prepared in nobIe gas matrices and studied using infrared spectroscopy and Hartree-Fock (SCF) calculations.The spectra indicate that two types of 1:1 complexes were formed, a normal one in which the hydrogen of HF is interacting with one hydrogen of silane or germane, and a reverse complex in which the fluorine of HF is interacting with one hydrogen atom of methane.The IR inactive symmetric C-H stretch in CH4 was observed in the CH4--FH complex as a weak band at 2914 cm-1.In the silane--HF and germane--HF complexes, the Si-H and Ge-H stretches were perturbed approximately 50 cm-1 to higher energy relative to the antisymmetric stretch ν3 in each parent molecule, but the ν1, modes were masked by the strong ν3 parent bands.Higher order 1:2 (AH4:HF) complexes were also observed and support the normal or reverse-type geometry of the 1:1 complexes.
Olah, G.,Kuhn, S. J.
, p. 164 - 165 (1959)
Slit jet infrared spectroscopy of hydrogen bonded N2HF isotopomers: Rotational Rydberg-Klein-Rees analysis and H/D dependent vibrational predissociation rates
Nesbitt, David J.,Lindeman, Theodore G.,Farrell, John T.,Lovejoy, Chris M.
, p. 775 - 785 (1994)
High resolution IR laser direct absorption spectra in a slit jet are presented and analyzed for nitrogen (15N14N-HF, 14N15N-HF, 15N15N-HF), and deuterium (14N14N-DF) substituted N2HF isotopomers.Both 14N15N-HF and 15N14N-HF isomers are observed, indicating a sufficiently deep minimum in the hydrogen bonding potential energy surface to quench internal rotation of the N2.The vibrationally averaged stretching potentials for each substituted species are recovered from rotational Rydberg-Klein-Rees (RKR) analysis.Features of the onedimensional (1D) potential surface such as hydrogen bond length (RH-bond), harmonic force constant (k?), and well depth (De) are then tested for isotopic invariance by direct comparison of the different isotopomers.Agreement among the various N substituted species for HF based complexes for either υHF = 0 or 1 is excellent, and provides effective 1D potentials for the stretching coordinate between 3.39 and 3.75 Angstroem.There is a 43 cm-1 (ca. 10percent) strengthening of the hydrogen bond upon HF vibrational excitation, as quantitatively reflected in the experimental redshifts and the shape of the RKR potentials for υHF = 0 and 1.The hydrogen bond is further strengthened by D/H isotopic substitution; this is a result of reduced vibrational averaging over DF vs HF bending motion, yielding a more linear, and hence stronger, hydrogen bond geometry.In contrast to the nearly apparatus-limited linewidths (Δνprediss ca 7 MHz) observed for each of the N2HF isotopomers, the N2DF complexes yield significantly broadened lines with 73 +/- 9 MHz homogeneous linewidths due to vibrational predissociation.This tenfold increase in predissociation rates upon deuteration is in contrast to previous measurements in other HF/DF containing complexes, and indicates the importance of a near resonant vibrational channel to form N2(υ = 1) + DF(υ = 0).The energetic accessibility of this V -> V channel would suggest an upper limit on the N2DF binding energy of D0 547 cm-1, which is also consistent with upper limits on D0 from the rotational RKR analysis.
Smith, D. F.
, p. 1040 - 1056 (1958)
Infrared Spectra of Amide-HF Complexes in Solid Argon
Bohn, Robert B.,Andrews, Lester
, p. 5684 - 5692 (1989)
Hydrogen-bonded complexes of amides and hydrogen fluoride have been prepared in solid argon.FTIR spectra of these complexes compared to spectra of similar carbonyl and amine complexes show that HF is hydrogen bonded to the carbonyl oxygen in the primary i
Reactions of formic acid methylester in the super acidic system XF/MF5 (X = H, D: M = As, Sb) and the crystal structure of HC(OH)(OCH3)+asf6-
Minkwitz, Rolf,Neikes, Frank,Ruettershoff, Dirk
, p. 2203 - 2207 (2000)
The reaction of formic acid methyl ester in the superacidic system XF/MF5 (X = H, D: M = As, Sb) leads to the hydroxy methoxy carbenium hexafluorometallates. The very hydrolysable and thermo labile salts are characterized by vibrational and NMR spectroscopic methods. Under inert conditions they are stable at -20°C for some weeks. HC(OCH3)(OH)+AsF6- crystallizes in the monoclinic space group P21/c (No. 14) with a = 5.275(1) A, b = 11.059(1) A, c = 12.113(1) A und β= 96.64(1)° and four formula units per cell.
The Existence of Tricyanomethane
Soltner, Theresa,H?usler, Jonas,Kornath, Andreas J.
supporting information, p. 13775 - 13776 (2015/11/11)
Calcium tricyanomethanide reacts with hydrogen fluoride under formation of tricyanomethane and Ca(HF2)2. Tricyanomethane is stable below -40 °C and was characterized by IR, Raman, and NMR spectroscopy. The vibrational spectra were compared to the quantum-chemical frequencies at the PBE1PBE/6-311G(3df,3dp) level of theory and confirm the predicted C3v symmetry of the molecule with regular C-H (109.8pm), C-C (146.7pm), and C-N (114.7pm) bonds.
