Calculation of the 14N and 2H quadrupole coupling tensor in trimeric imidazole

The ¹⁴N and ²H quadrupole coupling tensors at both nitrogen and at all hydrogen sites, have been calculated by ab initio SCF MO methods, in a trimeric imidazole molecule having the geometry found in the solid state. The ¹⁴N changes produced at N(1)H by hydrogen bonding are correctly reproduced to a noteworthy degree of precision, as is the ²H quadrupole interaction at the same site. The changes in the values of the three principal components of the tensor, which have been inferred from NQR measurements when imidazole passes from the gas to the solid state, are supported by the calculations, both for N(1)H and N(3).     

SiC-doped boron nitride nanotubes: computations of 11B and 14N quadrupole coupling constants

Abstract  

Density-functional theory calculations have been performed to investigate the properties of the electronic structures of silicon–carbon-doped boron nitride nanotubes (BNNTs). The geometries of zigzag and armchair BNNTs were initially optimized and the quadrupole coupling constants subsequently calculated. The results indicate that doping of B and N atoms by C and Si atoms has more influence on the electronic structure of the BNNTs than does doping of B and N atoms by Si and C atoms. The changes of the electronic sites of the N atoms are also more significant than those of the B atoms.     

The determination and assignment of a complete 14N quadrupole coupling tensor in liquid solution

¹⁴N line splittings in the spectrum of nitrobenzene (neat liquid) and metadinitrobenzene (dissolved in benzene), induced by an external electric field, have been used to determine the complete ¹⁴N quadrupole coupling tensor of these substances. Assuming that both molecules are rigid and planar, and that the quadrupole coupling tensors at the ¹⁴N nuclei are identical, the principal components in a local reference frame (x′, y′, z′) are (eQ/h)V_x′ x′ = ±0.34 MHz (eQ/h)V_y′_y′= ±1.18 Hz and (eQ/h)V_z′_z′ = ±1.52. The z′-direction is parallel to the CN bond and the y?direction is perpendicular to the plane of the nitrogroup. With these data the asymmetry parameter η = 0.55.     

An ab initio calculation of 14n quadrupole coupling constants

Ab initio SCF-MO calculations of ¹⁴N quadrupole coupling constants are reported for HCN, HNC, CH₃CN, CH₃NC, NH₃, NH₂NH₂, FCN, N₂O, (CN)₂, BrCN, pyridine and pyrazine. There is excellent correlation between calculation and experiment yielding Q = 1.503 ± 0.159 × 10^?26 cm² for the ¹⁴N nuclear quadrupole moment. Dunning sp basis sets are more than adequate for such calculations, STO/4G basis sets yielding almost identical results for pyridine and pyrazine. Unsuccessful attempts were made to correlate coupling constants with electronic population analysis indices.     

AB initio calculations of 2H and 14N quadrupolar coupling constants in hydrogen bonded dimers

SCF MO calculations at the 6-31G^** level of approximation are reported for ²H and ¹⁴N electric field gradients in HCN?HCN, HCN?HF, and CH₃CN?HF dimers, with emphasis on the configurational dependence of these quantities in (HCN)₂. In comparison with available experimental nuclear quadrupolar coupling constants, the calculated values for the monomers and dimers exhibit an accuracy of ≈ 10%, which is comparable to that of other spectroscopic parameters. The implications of hydrogen bonding for quadrupolar spin-lattice relaxation rates are briefly discussed.     

Microwave spectrum, 14N nuclear quadrupole coupling constants,dipole moment and centrifugal distortion constants of 2,6-difluoropyridine

The rotational and centrifugal distortion constants of 2,6-difluoropyridine have been determined from the analysis of its microwave spectrum. The dipole moment of the molecule and the quadrupole coupling constants of the ¹⁴N nucleus have also been evaluated. The observed rotational constants indicate a distortion of the pyridine ring.     

HPLC preparation of nitrate from ice cores for mass spectrometric 15N/14N measurements

Summary A method for the analysis of ¹⁵N-data of nitrate at ultratrace levels in ice cores is described. Samples are pre-concentrated using a HPLC-system. Nitrate is then reduced using the Dumas method to molecular nitrogen, which is analysed by mass spectrometry. The overall analytical precision of the method is ±0.4¹⁵N at a sample size of 35 bar l N₂. First results of deep ice-core analyses from Dome Summit, Greenland, are given.     

Ammonia-filled discharge tubes for optical emission spectrometric determination of 15N : 14N isotope ratios

A procedure is described for filling a discharge tube, permanently attached to a vacuum line, with ammonia in the pressure range 1.5–5 Torr, without any carrier gas. The ¹⁵N : ¹⁴N isotope ratio is determined from the N₂ spectrum emitted when the tube is excited by a 2450-MHz microwave source. Cooling one end of the discharge tube to —60°C enables the N₂ (1,0) bandheads at 316 nm to be used for ¹⁵N contents down to about 0.04 atom-%. Unidentified interfering bands and emission from NH, OH, H₂ and H are discussed. Samples containing 1–30 mg of nitrogen can be analysed with an accuracy and precision suitable for most soil—plant studies employing ¹⁵N as a tracer.     

Microwave spectrum of N2D4, 14N quadrupole coupling constants,and the barrier to inversion of the amino group

The microwave spectrum of N₂D₄ has been observed and analyzed. Based on five low-J rotational transitions the effective rotational constants are: A = 74712.9 ± 1.9 MHz, B = 18500.42 ± 0.46 MHz, and C = 18439.91 ± 0.46 MHz. The quadrupole coupling constants of the ¹⁴N nuclei are X_aa = 4.23 ± 0.04 MHz, X_bb = 1.98 ± 0.05 MHz, and X_cc = ?2.25 ± 0.05 MHz. Using the observed ground state inversion splittings for N₂D₄ and N₂H₄ the barrier to inversion of a single amino group is computed to be 5.00 kcal mol^?1.     

14N and 13C NMR of tautomeric systems of hydroxy-pyridines

¹⁴N NMR is shown to be an efficient method of investigation of the tautomeric equilibria in hydroxy-and related substituted pyridines. Large relative ¹⁴N chemical shifts within tautomeric pairs estimated from N-Me and O-Me derivatives make possible quantitative determinations of the equilibria. Qualitative conclusions may be drawn from ¹⁴N line widths as well as from ¹³C and proton chemical shifts.     

14N NMR弛豫法研究3-烷基斯德酮

常温下3-丙基斯德酮和3-丁基斯德酮为具有很高介电常数的液体，与许多溶剂混溶，预期可以作为许多电解质的优良溶剂．斯德酮环3位上的氮原子给出尖锐的~(14)N NMR峰．~(14)N的四极矩弛豫时间T_Q＝T_2．利用变温下~(14)N NMR T_2测量，得出这两个化合物成液态时分子运动活化能．结果与粘度测量法所得的吻合．     

14N Nuclear quadrupole interaction in Cu(II) doped l-alanine

The ¹⁴N nuclear quadrupole interaction tensor P_N measured by ENDOR in Cu(II) doped l-alanine is analyzed in terms of the Townes and Dailey theory assuming a tetrahedrally bonded N atom. The results of this analysis are compared with those for the ¹⁴N in pure l-alanine and it is found that the principal directions of the P_N tensor are drastically changed upon metal complexation as a consequence of the higher electron affinity of Cu(II) with respect to C and H. Comparison of the corresponding bond populations in pure and Cu(II) doped l-alanine indicates that the Cu draws 0.11 more electron from the N than the substituted H atom.     

Microwave spectrum,conformation, intramolecular hydrogen bond,dipole moment, 14N quadrupole coupling constants and centrifugal distortion of 2flu

Microwave spectra of CH₂FCONH₂, CH₂FCOND(1)H(2), CH₂FCONH-(1)D(2), and CH₂FCOND₂ are reported. The stable form of the molecule is shown to possess a planar FCCONH₂ skeleton, with two out-of-plane hydrogens. The C-F and CO bonds are trans to one another and a weak intramolecular hydrogen bond is formed between the fluorine atom and the nearest amide group hydrogen atom stabilizing the identified rotamer. Other conformations are not present in concentrations exceeding 10% of the total. Nine vibrationally excited states were assigned. Six of these were attributed to the C-C torsional mode and one to the lowest in-plane bending mode. The first excited state of -NH_z out-of-plane deformation mode was tentatively assigned. Relative intensity measurements yielded 114±14 cm^?1 for C-C torsional mode and 239±20 cm^?1 for the in-plane bending mode. The dipole moment was determined asμ_a = 1.27±0.01 D, μ_b = 1.67±0.02 D, and μ_tot = 2.10±0.02 D, while the ¹⁴N quadrupole coupling constants were found to be χ_aa = 1.6±0.2 MHz, χ_bb = 1.6±0.2 MHz and χ_cc = ?3.2±0.3 MHz.     

14N NQR and phase transitions in tetracyanoquinodimethanide alkaline salts

¹⁴N NQR lines of RbTCNQ and NaTCNQ polycrystalline samples, measured as a function of temperature, show small but sharp discontinuities at the regular-alternant phase transition (found respectively at 214 K and 346 K), together with the expected change in spectral multiplicity. No ν^? lines were detected in NaTCNQ. Co-existence of phases, more marked in NaTCNQ, shows up in NQR data.The use of a pulsed, FT spectrometer yields estimates of T₁ relaxation time: it shows no discontinuity at the phase transition, is around 1 ms at room temperature for ν+ lines, more than 2 order of magnitudes larger for ν^? lines, increases smoothly on decreasing temperature.     

Effects of chemical shift anisotropy and 14N coupling on the 1H and 195Pt nuclear magnetic resonance spectra of platinum complexes

Broadening of the ¹⁹⁵Pt satellites in the ¹H NMR spectrum of trans-Pt(ethene)(2-carboxy-pyridine)Cl₂ at high field arises from relaxation of ¹⁹⁵Pt via the chemical shift anisotropy mechanism. We also demonstrate that well-resolved ¹⁴N-¹⁹⁵Pt couplings can be observed in ¹⁹⁵Pt NMR spectra of Pt(II) and Pt(IV) amine complexes, including anti-tumour agents, at elevated temperature where scalar coupling contributions to ¹⁹⁵Pt relaxation are much reduced.     

15N/14N Isotopic Exchange in the Dissociative Adsorption of N2 on Tantalum Nitride Cluster Anions Ta3N3-

Adsorption and activation of dinitrogen (N₂) is an indispensable process in nitrogen fixation. Metal nitride species continue to attract attention as a promising catalyst for ammonia synthesis. However, the detailed mechanisms at a molecular level between reactive nitride species and N₂ remain unclear at elevated temperature, which is important to understand the temperature effect and narrow the gap between the gas phase system and condensed phase system. Herein, the ¹⁴N/¹⁵N isotopic exchange in the reaction between tantalum nitride cluster anions Ta₃¹⁴N₃^- and ¹⁵N₂ leading to the regeneration of ¹⁴N₂/¹⁴N¹⁵N was observed at elevated temperature (393-593 K) using mass spectrometry. With the aid of theoretical calculations, the exchange mechanism and the effect of temperature to promote the dissociation of N₂ on Ta3N3? were elucidated. A comparison experiment for Ta₃¹⁴N₄^-/¹⁵N₂ couple indicated that only desorption of ¹⁵N₂ from Ta₃¹⁴N₄¹⁵N₂^- took place at elevated temperature. The different exchange behavior can be well understood by the fact that nitrogen vacancy is a requisite for the dinitrogen activation over metal nitride species. This study may shed light on understanding the role of nitrogen vacancy in nitride species for ammonia synthesis and provide clues in designing effective catalysts for nitrogen fixation.     

The 14N quadrupole broadening of the hydride 1H NMR pattern in trans-[PtH(NCS) (PEt3)2]

One of the sets of hydride ¹H NMR patterns for the isothiocyanato/thiocyanato mixture trans- [PtH(SCN) (PEt₃)₂] is broad. Previously there had been disagreement on the cause of this broadening. It is now shown to be due to the ¹⁴N quadrupole by double resonance.     

The pheophytin a anion radical. 14N and 1H endor and triple resonance in liquid solution

From electrolytically generated phcophytin a anion radicals in solution, 12 proton and 2 nitrogen hyperfine coupling constants, including signs, were determined by ENDOR and TRIPLE resonance and interpreted by MO calculations. The data are compared with those from the anion radicals of chlorophyll a and the bacterial analogues bacteriopheophytin a and bacteriochlorophyll a.