Determination of the cubic force field of nitrosyl fluoride by vibration-rotation α constants and sextic centrifugal distortion constants

Summary The rotational spectra of ONF in the (100), (010) and (001) excited vibrational states were observed and the corresponding vibrationratation α constants determined. A centrifugal-distortion analysis of 156 ground-state rotational transitions yielded accurate values of all the sextic centrifugal-distortion constants. Both vibration-rotation α constants and sextic centrifugal-distortion constants were used to determine, by least-squares methods, the cubic part of the general valence force field of nitrosyl fluoride. Anab initio calculation provided reliable constraints for the three cubic terms of the potential-energy function which are not directly determinable by the available experimental data. Supporting organizations: C.N.R. and M.P.I.     

14N chemical shifts and quadrupole coupling constants of inorganic nitrates

The isotropic chemical shift and the nuclear quadrupole coupling constant for (14)N were obtained for 14 inorganic nitrates by solid-state MAS NMR measurements at two different field strengths, 9.4 and 11.7 T. The compounds studied were polycrystalline powders of AgNO(3), Al(NO(3))(3), Ba(NO(3))(2), Ca(NO(3))(2), CsNO(3), KNO(3), LiNO(3), Mg(NO(3))(2), NaNO(3), Pb(NO(3))(2), RbNO(3), Sr(NO(3))(2), Th(NO(3))(4)center dot4H(2)O, and UO(2)(NO(3))(2)center dot3H(2)O. Even though the spectra show broadening due to (14)N quadrupole interactions, linewidths of a few hundred hertz and a good signal-to-noise ratio were achieved. From the position of the central peaks at the two fields, the chemical shifts and the nuclear quadrupole coupling constants were calculated. The chemical shifts for all compounds studied range from 282 to 342 ppm with respect to NH(4)Cl. The nuclear quadrupole coupling constants range from 429 kHz for AgNO(3) to 993 kHz for LiNO(3). These data are compared with those available in the literature.     

14N and35Cl nuclear quadrupole double resonance study of the structural phase transitions in N-octylammoniumchloride

The structural phase transitions between the non-intercalated phases of the layer structure compound N-octylammoniumchloride have been studied via proton-¹⁴N and proton-³⁵Cl nuclear quadrupole double resonance. The results have been related to an order-disorder model of the octylammonium chains. The temperature dependence of the order parameters of the –NH₃ head groups has been determined.     

14N and35Cl nuclear quadrupole double resonance study of the phase transitions in n-decylammoniumchloride and n-hexylammoniumchloride

The structural phase transitions between the intercalated and the non-intercalated phases of the layer structure compound n-decylammoniumchloride and n-hexylammoniumchloride have been studied via proton-¹⁴N and proton-³⁵Cl nuclear quadrupole double resonance. The results have been related to an order-disorder model of the alkylammonium chains. The temperature dependence of the order parameters of the –NH₃ head groups has been determined.     

Internal rotation and chlorine nuclear quadrupole coupling of o-chlorotoluene studied by microwave spectroscopy and ab initio calculations

The microwave spectrum of o-chlorotoluene has been reinvestigated using molecular beam Fourier transform microwave (MB-FTMW) spectrometers in the frequency range of 4–23 GHz. Due to the high resolution of this molecular beam technique the analysis yielded improved rotational constants, centrifugal distortion constants, and, for the first time, the complete chlorine nuclear quadrupole coupling tensor. From the torsional fine structure the barrier to internal rotation of the methyl group was found to be 5.5798(52) kJ mol⁻¹. Experimental results and ab initio calculations are compared.     

Molecular motions in chloramphenicol studied by35Cl nuclear quadrupole and1H nuclear magnetic resonance spectroscopy

The³⁵Cl nuclear quadrupole resonance (NQR) frequency (v_Q), nuclear quadrupole spinlattice relaxation time (T_1Q),¹H nuclear magnetic resonance second moment (M₂) and nuclear magnetic spin-lattice relaxation timeT ₁) were measured for polycrystalline chloramphenicol (drug) as a function of temperature. Hindered rotation of the CHC1₂ group and the phenyl ring was detected, the relevant activation energies were determined. The rotations are discussed in detail.     

The microwave spectrum,barrier to internal rotation of the methyl group,and N nuclear quadrupole coupling constants in methacrylonitrile

The microwave spectrum of methacrylonitrile has been assigned and frequencies are listed in the 8–40 GHz frequency region for the assigned transitions. The rotational constants are A = 9297.48 ± 0.30, B = 4166.33 ± 0.01, and C = 2924.68 ± 0.01 all in units of MHz. The barrier to internal rotation of the methyl group is V₃ = 2030 ± 60 cal/mole. The ¹⁴N nuclear quadrupole coupling constants are χ_aa = −4.18 ± 0.04 and χ_bb = 2.03 ± 0.15 in units of MHz.     

14N Nuclear quadrupole coupling and methyl internal rotation in the microwave spectrum of 2-methylpyrrole

Using two molecular jet Fourier transform microwave spectrometers, the rotational spectrum of 2-methylpyrrole was recorded in the frequency range from 2 to 40?GHz. From the torsional splittings due to the internal rotation of the methyl group a barrier height of 279.7183(26) cm^?1 was deduced. Because of the ¹⁴N nucleus, all lines show a quadrupole hyperfine structure. The microwave spectra were analysed using the XIAM and BELGI-C_s-hyperfine codes. The XIAM code enabled us to reproduce the whole data set with a root-mean-square deviation of 5.6 kHz while the BELGI-C_s-hyperfine code could provide a better root-mean-square almost by a factor of 2 compared to that of XIAM. The experimental results were complemented by quantum chemical calculations. The values of the methyl torsional barrier and the ¹⁴N nuclear quadrupole coupling constants are discussed and compared with other methyl substituted pyrroles as well as other aromatic five-membered rings.     

A molecular beam Fourier transform microwave study of 2-methylpyridine and its complex with argon: structure,methyl internal rotation and 14N nuclear quadrupole coupling

The rotational spectrum of 2-methylpyridine (α-picoline, CH₃C₅H₄N) in the two lowest levels of methyl internal rotation (m=0, ±1) has been recorded in the frequency range from 2 to 15 GHz using a molecular beam Fourier transform microwave spectrometer. The high resolution and sensitivity of this spectroscopic technique allowed resolution of hyperfine structures due to ^l4N nuclear quadrupole coupling with high accuracy and detection of the spectra of the ¹⁵N- and all ¹³C-isotopomers. These investigations considerably extend the results from an earlier study on the normal species (Dreizler, H., Rudolph, H. D., and Mader, H., 1970, Z. Naturforsch., 25a, 25); improved rotational and centrifugal distortion constants as well as all components of the ¹⁴N quadrupole coupling tensor have been obtained. Analysis of the spectra of the isotopomers yielded the ^I4N quadrupole coupling constants χ _cc and χ _aa – χ _bb (for the ¹³C species), the potential parameter V ₃ for the barrier hindering the internal rotation of the methyl group, and, in particular, r_o, r_s r _m ⁽¹⁾ and r _m ⁽²⁾ structural parameters for the molecule. In addition to the microwave studies on the monomer, we have also investigated the rotational spectrum of the weakly bound dimer of normal 2-methylpyridine with Ar. The results obtained for the quadrupole coupling constants and the hindering potential for the internal methyl rotation show that the corresponding parameters are not significantly, or only slightly, changed in the complex.     

Chlorine nuclear quadrupole coupling in chlorodifluoroacetyl chloride: Theory and experiment

A potential energy scan of chlorodifluoroacetyl chloride, CF₂ClC(O)Cl, at the MP2/6-311+G(d) level of theory predicts stable gauche and trans conformers, with E_gauche<E_trans. Ab initio calculations were made of approximate equilibrium structures of these and, on these structures, calculations were made of ³⁵Cl and ³⁷Cl nuclear quadrupole coupling constant tensors. Coupling constants here predicted, as well as rotational constants and molecular dipole moments, are applied to aid analyses of experimental microwave spectra. Chirped pulse Fourier transform microwave spectroscopy has been used to rapidly record the rotational spectra of four isotopologues of the title molecule, CClF₂C(O)Cl, namely ³⁵Cl³⁵Cl, ³⁵Cl³⁷Cl, ³⁷Cl³⁵Cl, and ³⁷Cl³⁷Cl. Only the gauche conformer was observed under the experimental conditions. For the four isotopologues a total of 464, 219, 197, and 77 transitions have been recorded, respectively. With the exception of the ³⁷Cl³⁷Cl isotopologue sufficient data was available to determine all Cl quadrupole coupling tensors. Comparisons between the theoretical and experimental results are made.     

Fourier transform microwave spectroscopy of isotopically substituted diacetylenes: rs-structure, quadrupole coupling, and anisotropic nuclear spin-spin interaction

Monodeuterated diacetylene (HCCCCD) and its ¹³C-substituted species H¹³CCCCD, HC¹³CCCD, HCC¹³CCD, and HCCC¹³CD were investigated by Fourier transform microwave spectroscopy. The D nuclear quadrupole splittings were almost completely resolved. For H¹³CCCCD hyperfine splittings caused by the anisotropic nuclear spin-spin interaction between the H and ¹³C nuclei were also observed. The analysis yielded rotational constants, centrifugal distortion constants, and the constants for the nuclear quadrupole coupling and anisotropic nuclear spin-spin interaction. The substitution structure of HCCCCD was calculated as follows: r_s(C-H) = 1.056054(39) Å, r_s(CC) = 1.208631(4) Å, r_s(C-C) = 1.374117(6) Å, r_s(CC) = 1.208116(4) Å, and r_s(C-D) = 1.056231(17) Å, in the order of the arrangement of the bonds. A rough estimate of the equilibrium structure is also presented. The eQq constant for the deuterium nucleus is 0.2061(4) MHz. The anisotropic ¹³C-H spin-spin interaction constant was experimentally determined for the first time as b = −29.2(15) kHz, which is defined as the coefficient of (3I_2zI_3z − I₂ · I₃), where I₂ and I₃ denote the H and ¹³C nuclear spins, respectively, and I_2z and I_3z their components along the molecular axis. The observed b constant is not accounted for by the direct magnetic dipole-dipole interaction only, suggesting a significant contribution from indirect anisotropic interaction.     

Nuclear relaxation,molecular motions and interactions. Part II. 14N nuclear quadrupole relaxation from the1H line-shape analysis,and viscosity measurements of pyrrole in “non-active” solvents

The ¹⁴N relaxation time of pyrrole in cyclohexane, carbon tetrachloride and pentafluororyridine solution has been determined at a number of temperatures through a line-shape analysis of the imido proton pmr signal of pyrrole (scalar relaxation of the second kind). The viscosity of pyrrole in the same solvents has also been measured. The results are discussed in terms of solvent effects on the association equilibria of pyrrole.     

Cl nuclear quadrupole resonance studies of molecular motions of ClO3 and water diffusion in Ca(ClO3)2·2H2O

A ³⁵Cl nuclear quadrupole resonance (³⁵Cl-NQR) investigation of polycrystalline Ca(ClO₃)₂·2H₂O is described. The ³⁵Cl-NQR frequencies (ν_Q) for two resonance lines (ν_Q1 and ν_Q2), the spin lattice relaxation time (T_1Q) for ν_Q2 only and the line width δν_Q2 were measured in the temperature range 292–345 K, except for the frequency measured up to 455 K. The observed decrease in the resonance frequencies with increasing temperature permitted the determination of the frequencies of librations of the ClO₃⁻ ion about two axes perpendicular to the three-fold axis of the ion mainly responsible for this effect. The temperature dependence of the relaxation time T_1Q proved the occurrence of water diffusion and hindered rotation of ClO₃⁻ ions. The activation energies of these two molecular motions were determined, and their effect on the electric field gradient at the site of a chlorine nucleus was discussed. Temperature measurements of the line width δν_Q2 confirmed the conclusions drawn from the analysis of T_1Q(T).