Deuteron quadrupole coupling in formaldehyde

The hyperfine structure of the 1₁₀-1₁₁ rotational transition of D₂CO has been observed with a beam-maser spectrometer and the spin-rotation and electric quadrupole coupling constants have been determined. Using previously reported measurements on HDCO, the complete electric field gradient tensor at the position of the deuteron has been evaluated.     

Roton-rotation coupling of acetylene in 4He

Rotational absorption spectra of acetylene in superfluid 4He calculated using a path-integral correlation function approach are seen to result in an anomalously large distortion constant in addition to a reduced rotational constant, with values in excellent agreement with recent experiments. Semianalytic treatment of the dynamics with a combined correlated basis function-diffusion Monte Carlo method reveals that this anomalous behavior is due to strong coupling of the higher rotational states of the molecule with the roton and maxon excitations of 4He, and the associated divergence of the 4He density of states in this region.     

Radiofrequency spectroscopy inside a laser cavity: Nuclear quadrupole resonance and A1-A2 splitting of CH3Br

The highly sensitive method of infrared-radiofrequency double resonance inside a CO₂N₂O laser cavity has been applied to the observation of “pure” nuclear quadrupole resonance and direct A₁-A₂ transitions of CH₃Br. More than 150 quadrupole resonances have been observed for ¹²CH₃⁷⁹Br, ¹²CH₃⁸¹Br, ¹³CH₃⁷⁹Br, and ¹³CH₃⁸¹Br using direct double resonance as well as collision-induced satellites. Accurate hyperfine constants, i.e., the quadrupole coupling constant eqQ and its rotational dependence χ_J and χ_K, Hougen's coefficient χ_d, and the spin-rotation constants C_N and C_K have been determined for the ground state. The eqQ in the excited states ν₃, ν₆, ν₃ + ν₆, and 2ν₆ have also been determined. About 60 direct l-doubling transitions have been observed, which has enabled us to determine the l-doubling constant q_v(1,1), its rotational dependence δq_v^J(1,1) and the asymmetry parameter for the quadrupole coupling constant eqQη for the ν₆ and ν₃ + ν₆ states. A set of direct A₁-A₂ transitions in the 2ν₆ state with K = 1 and l₆ = ?2 and that in the ν₆ state with K = 2 and l₆ = ?1 have been observed. The rovibrational and isotope assignments of the observed A₁-A₂ are helped by the existence of quadrupole hyperfine structure and many collision-induced satellites. The rovibrational assignments of CH₃Br transitions which are coincident with laser lines are summarized.     

Microwave spectrum of and quadrupole coupling in isopropyliodide

The microwave spectrum of isopropyliodide was studied in the 18.0 to 26.5 GHz region. From observed a-type R-transitions, the rotational constants A, B, C and the quadrupole coupling constants χ_aa, χ_bb, χ_cc, and χ_ac were determined using diagonalization of the complete Hamiltonian matrix including all quadrupole operator matrix elements. The results are consistent with those of the homologous series (CH₃)_nCH_3?nI, n = 0, 1, 2, 3.     

Molecular structure, nuclear quadrupole coupling constant and dipole moment of nitrogen trichloride from microwave spectroscopy

The rotational constants of four isotopic species of nitrogen trichloride have been obtained from transitions in the millimeter region. Two r_s structures have been obtained with the following average values of the parameters. rN−C1=1.7535 ± 0.0020 A.The Stark effect of the J = 3 ← 2 transition was analyzed to obtaine the value 0.39 ± 0.01 D for the dipole moment of NCl₃. The measurement of the separation of the two strongest hyperfine components of the J = 2 ← 1 transition yielded the value of −108 ± 3 MHz for the N---Cl bond axis quadrupole coupling constant.     

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.     

Measurement of Cl and N quadrupole coupling in ClCN

J = 1 ← 0 and J = 2 ← 1 transitions in ³⁵ClCN and ³⁷ClCN were measured using a C-band waveguide spectrometer and phase-locked sources. Parameters obtained from the data are: $\text{B(}{}^{35}\text{ClCN) = 5 970.820 ± 0.010 MHz}$, $\text{B(}{}^{37}\text{ClCN) = 5 847.246 ± 0.008 MHz}$, $\text{eqQ(}{}^{35}\text{Cl) = ?83.26 ± 0.04 MHz}$, $\text{eqQ(}{}^{37}\text{Cl) = ?65.61 ± 0.04 MHz}$ and $\text{eqQ(}{}^{14}\text{N) = ?3.60 ± 0.08 MHz}$.     

Nuclear quadrupole coupling in the microwave spectrum of imidazole

The quadrupole hyperfine structure in the rotational spectrum of two isotopic forms of imidazole has been analyzed to obtain principal nuclear quadrupole coupling constants for the two nonequivalent nitrogen atoms. The results have been compared with field gradient tensors calculated using INDO molecular orbital wavefunctions and some implications for the electronic structure of imidazole are mentioned. Comparisons with pyrazole and the NQR results for imidazole are also made.     

Diode laser spectroscopy of overtone bands of acetylene

Overtone absorption lines of acetylene in the regions around 12700 and 11800 cm^–1 have been examined by the use of tunable diode lasers in free-running mode. The diode laser emission wavelength was scanned around the gas resonances by simply sweeping its injection current, permitting a direct observation of the absorption line-shapes. Weak overtone absorption lines have been detected by using the wavelength modulation (WM) spectroscopy with 2nd harmonic detection technique and the collisional broadening and shift coefficients have been obtained. The high resolving power and accuracy of the spectrometer permitted a wavenumber error of less than 0.01 cm^–1. The correct interpretation of the absorption signals when detecting the second harmonic in the presence of a sloping background is discussed.     

Nuclear quadrupole coupling interactions in the rotational spectrum of tryptamine

Four conformers of tryptamine have been detected in a supersonic expansion and characterized by laser ablation molecular beam Fourier transform microwave spectroscopy LA-MB-FTMW in the 5–10 GHz frequency range. The quadrupole hyperfine structure originated by two ¹⁴N nuclei has been completely resolved for all conformers and used for their unambiguous identification. Nuclear quadrupole coupling constants of the nitrogen atom of the side chain have been used to determine the orientation of the amino group involved in N–H?π interactions: to the π electronic system of the pyrrole unit in the Gauche-Pyrrole conformers (GPy) or to the phenyl unit in the Gauche-Phenyl ones.     

Nuclear quadrupole coupling in the microwave spectrum of 1,2,3-triazole

The hyperfine structure in the microwave spectra of 1,2,3-triazole and N-deutero 1,2,3-triazole has been analyzed. The coupling constants derived from the analysis of each isotopic species have been combined to give the principal nuclear quadrupole coupling constants at the sites of the three inequivalent ¹⁴N nuclei.     

Difference-frequency laser spectroscopy detection of acetylene trace constituent

5 sbandpectrum. Spectroscopic detection of 28 ppmm/Hz^1/2 was performed. This corresponds to a minimum detectable mixing ratio of ∼1 ppb in conjunction with a 100-m White cell and balanced detection. Received: 3 April 1998/Revised version: 5 June 1998     

Density functional theory calculations of nuclear quadrupole coupling constants with calibrated 14N quadrupole moments

Density functional calculations of the electric field gradient tensor at the nitrogen nucleus in 13 test molecules, containing 14 nitrogen sites, have been performed using the linear combination of Gaussian-type orbital Kohn-Sham density functional theory (LCGTO-KSDFT) approach. Local and gradient corrected functionals were used for all-electron calculations. All the molecular structures were optimized at their respective levels of theory with extended basis sets. Calibrated ¹⁴N nuclear quadrupole moments were obtained through a fitting procedure between calculated electric field gradients and experimental nuclear quadrupole coupling constants of the test set of molecules for each basis set and functional considered. With these calibrated ¹⁴N nuclear quadrupole moments, the nuclear quadrupole coupling constants of the following selected systems were determined: fluoromethylisonitrile, pyridine, pyrrole, imadazole, pyrazole, 1,8-bis(dimethyl-amino)naphthalene, cyclotetramethylenetetranitramine, cocaine and heroin.     

14N and35Cl nuclear quadrupole coupling constants in thiazyl chloride from microwave spectroscopy andab initio molecular orbital computations

Summary The¹⁴N and³⁵Cl nuclear quadrupole coupling constants of the¹⁴N³²S³⁵Cl isotopic species of thiazyl chloride have been determined from an analysis of the hyperfine structure of sixμ _a andμ _b transitions in the microwave spectrum as (in MHz) _χaa (³⁵CL) = −39.00(3), _χbb (³⁵CL) = 23.84(4), _χaa (¹⁴N) = −1.42(6), _χbb (¹⁴N) = −4.16(6).

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Riassunto Le costanti di accoppiamento quadrupolare di¹⁴N e³⁵Cl della specie isotopica¹⁴N³²S³⁵Cl del tiazil cloruro sono state determinate attraverso l'analisi della struttura iperfine di sei transizioni di tipoμ _a eμ _b dello spettro a microonde. Si sono ottenuti i seguenti valori (in MHz): _χaa (³⁵CL) = −39.00(3), _χbb (³⁵CL) = 23.84(4), _χaa (¹⁴N) = −1.42(6), _χbb (¹⁴N) = −4.16(6).

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Резюме Из анализа сверхтонкой структуры шестиμ _a иμ _b переходов в микроволновом спектре определяются ядерные квадрупольные константы связи¹⁴N и³⁵Cl в¹⁴N³²S³⁵Cl. Получены следующие значения (в МГц): _χaa (³⁵CL) = −39.00(3), _χbb (³⁵CL) = 23.84(4), _χaa (¹⁴N) = −1.42(6), _χbb (¹⁴N) = −4.16(6).kg]PACS. 33.20

     

Deuteron quadrupole coupling constants in crystals with symmetrical hydrogen bonds

Deuteron quadrupole coupling constants for the free formic and trifluoroacetic acid molecules, for their acid anions and for the maleate anion were calculated using the INDO method. The results are compared with experimental values for potassium deuterium maleate and bistrifluoroacetate.     

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.     

The Stark effect in molecules with strong nuclear quadrupole coupling

The Hamiltonian for a rotating molecule containing one nuclear quadrupole in a uniform electric field is H ₀ + H_E + H_Q , where H ₀ describes the unperturbed rotator, H_E the interaction with the electric field and H_Q the coupling of the nuclear quadrupole to the rotating molecule. The energy is evaluated, up to and including terms in H_EH_Q in symmetric tops in which the quadrupolar nucleus is on the axis, and H_E ² H_Q in linear molecules, by treating H_E and H_Q as perturbations to H ₀. Dipole moments determined through studies of the Stark effect in microwave spectra can be significantly affected by the higher-order terms, even in weak electric fields, if the nuclear quadrupole coupling energy is not small relative to the separation of the rotational energy levels.

Dipole moments determined from Stark splittings of the J = 2←J = 1 lines are reduced by approximately 1 per cent in AsF₃ and from 1·647 to 1·618D in CH₃I.