The Lamb-dip spectrum of the J = 1 ← 0 transition of DF: Crossing resonances and hyperfine components

The Lamb-dip technique has been applied to the observation of the J = 1 ← 0 transition of DF: for the first time, the hyperfine structure due to D and F have been resolved by using microwave spectroscopy. The high accuracy of this technique allows us to provide hyperfine parameters that are in very good agreement with those obtained from molecular beam experiment. In addition, our frequencies together with the unresolved ones up to J″ value of 47 allow us to provide the most accurate ground state rotational constants of DF known at the moment. Furthermore, due to the presence of a relevant number of strong crossing resonances, the J = 1 ← 0 transition of DF can be considered an illustrative case to show how they modify the shape of Lamb-dip spectra.     

The Lamb-dip spectrum of phosphine: The nuclear hyperfine structure due to hydrogen and phosphorus

For the first time, the hyperfine structure of the rotational J = 1 ← 0 (K = 0) and J = 2 ← 1 (K = 0, 1) transitions of phosphine has been resolved by using microwave spectroscopy. To this purpose, the Lamb-dip technique has been employed. In addition, the J = 3 ← 2 (K = 0, 1, 2) transition has been recorded at Doppler resolution. The present investigation allowed us to provide accurate values for most of the hyperfine constants as well as ground state rotational parameters.     

Hyperfine structure of the J=1←0 transition of HCl and HCl: improved ground state parameters

The pure rotational J=1←0 transitions of H³⁵Cl and H³⁷Cl have been observed in the millimeter-wave region using the Lamb-dip technique to resolve the hyperfine structure due to ³⁵Cl or ³⁷Cl and H. The present observations allow to provide not only very accurate hyperfine constants but also, joint together with previous data, the most accurate ground state rotational parameters known up to now. The experimental determination of the hyperfine parameters has also been supported by ab initio computations.     

The magnetic hyperfine structure in the rotational spectrum of H2CNH

The hyperfine structure in the ground-state rotational spectrum of methanimine was studied in the frequency range of 64-172 GHz by means of the Lamb-dip technique. This allowed to resolve, in some hyperfine components due to the ¹⁴N nucleus, doublets separated by only some tenth of kHz. We explain the splittings as due to magnetic interactions of the three protons with their molecular environment. The analysis of the experimental spectrum has been guided by quantum-chemical calculations of the hyperfine parameters.     

Lineshape analysis of the J = 3 ← 2 and J = 5 ← 4 rotational transitions of room temperature CO broadened by N2, O2, CO2 and noble gases

Collisional relaxation has been considered for millimeter lines of carbon monoxide at room temperature. Accurate measurements of carbon dioxide- and rare gases-broadened widths have been performed on the J = 3 ← 2 rotational line of ¹²CO by using a video-type spectrometer. Measurements of nitrogen-, oxygen-, and xenon-broadened widths of the J = 5 ← 4 rotational line of ¹³CO were also carried by using a frequency-modulated spectrometer. A lineshape study performed on all the investigated binary systems provide confirmation that Voigt profile is not a suitable model to analyse experimental lines in the millimeter-waves region. On one hand, using this profile in the low pressure range, i.e. in the Doppler regime, the retrieved collisional linewidths do not follow a linear variation with the perturbing gas pressure. On the other hand, regardless of the pressure, lineshapes exhibit a narrowed profile. An accurate analysis of the pressure dependence of relaxation rates show that the Galatry profile is not appropriate and that experimental lineshapes are actually Speed Dependent Voigt profiles. Accurate broadening parameters were retrieved from this profile and compared to previous reported values and predictions calculated from the Robert-Bonamy formalism. Finally a variation of the ratio of relaxation speed dependence to broadening parameters versus relative masses of the collision partners is presented.     

Ground state rotational spectrum of nitrogen trifluoride: The K = 3 splittings of NF3 and NF3

The ground state rotational spectrum of the ¹⁴NF₃ and ¹⁵NF₃ isotopic species of nitrogen fluoride has been observed in the ∼450-810 GHz frequency range. This investigation allowed us to improve the rotational parameters for both isotopologues. In particular, for the first time the K = 3 line splitting parameter and the sextic centrifugal distortion constants have been determined for ¹⁵NF₃.     

N2-, H2-, and He-induced collisional broadening of the J = 24 ← 23 transition of HC3N located near 218.3 GHz at different temperatures

We report on experimental collisional relaxation of the J = 24 ← 23 line of HC₃¹⁴N, located near 218.3 GHz, induced by nitrogen, hydrogen, and helium. The measurements were carried out at selected temperatures in the 235-350 K range using a video-type spectrometer. The foreign gas broadening parameters and their temperature dependences were determined assuming Voigt lineshape profiles and the usual T⁻ⁿ temperature law. The experimental broadening parameters are compared with results derived using the ATC collisional formalism.     

Thermodynamic investigations of ternary o-toluidine + tetrahydropyran + N,N-dimethylformamide mixture and its binaries at 298.15, 303.15 and 308.15 K

The densities ρ, speed of sound u, data of o-toluidine (i) + tetrahydropyran (j) + N,N-dimethylformamide (k) and its {tetrahydropyran (j) + N,N-dimethylformamide (k); o-toluidine (i) + N,N-dimethylformamide (k)} binaries have been measured as a function of composition at 298.15, 303.15 and 308.15 K. The excess molar enthalpies, H^E data of same set of binary mixtures have also been measured over entire composition at 308.15 K. The densities and speeds of sound data of binary and ternary mixtures have been utilized to determine their excess molar volumes, V^E and excess isentropic compressibilities, κ_S^E. The observed thermodynamic properties of binary and ternary mixtures have been analyzed in terms of Graph theory. It has been observed that Graph theory correctly predicts the sign as well as magnitude of thermodynamic properties.     

Diode laser absorption spectra of HCCD and HCCD at 6500 cm

The absorption spectra of H¹²C¹³CD and H¹³C¹²CD have been observed at high resolution between 6480 and 6610 cm⁻¹ using an external cavity diode laser. The strong 2ν₁ band has been observed for each species using a sample enriched in deuterium at natural abundance of ¹³C. Rotational analyses reveal bands of both species to be essentially unperturbed. Centers of unblended lines are determined with an accuracy of approximately 10 MHz.     

K-Dependence and temperature dependence of N2-, H2-, and He-broadening coefficients for the J = 12-11 transition of acetonitrile CH3CN located near 220.7 GHz

Extensive experiments on the K = 3 component of the J = 12-11 rotational transition of acetonitrile CH₃C¹⁴N, located near 220.7 GHz, were performed at different temperatures in the range 235-350 K. They allow determining the N₂-, H₂-, and He-broadening coefficients, as well as their temperature dependences. More specific measurements on all the K-components of the involved transition perturbed by N₂ at 303 K allow to point out a clear decreasing of the broadening coefficient with increasing K. Narrowing effects are clearly observed, and experimental lines were analysed both with Voigt and speed dependent Voigt profiles; but no exhaustive lineshape study was carried out. All the experimental parameters are compared with results derived from a semiclassical calculation of collisional interactions, including electrostatic, induction, and dispersion energy contributions.     

The ν1 + 3ν2 + 3ν3 and 4ν1 + ν2 + ν3 bands of ozone by CW-cavity ring down spectroscopy between 5900 and 5960 cm

The absorption spectrum of ozone, ¹⁶O₃, has been recorded in the 5903-5960 cm⁻¹ region by high sensitivity CW-cavity ring down spectroscopy (α_min ∼ 5 × 10⁻¹⁰ cm⁻¹). The ν₁ + 3ν₂ + 3ν₃ and 4ν₁ + ν₂ + ν₃ A-type bands centred at 5919.15 and 5947.07 cm⁻¹ were newly observed. A set of 173 and 168 energy levels could be experimentally determined for the (1 3 3) and (4 1 1) states, respectively. Except for a few K_a = 5 levels of the (4 1 1) state, the rotational structure of the two states was found mostly unperturbed. The spectroscopic parameters were determined from a fit of the corresponding line positions by considering the (1 3 3) and (4 1 1) states as isolated. The determined effective Hamiltonian and transition moment operators were used to generate a list of 785 transitions given as Supplementary Material.     

Laser spectroscopy of holmium monosulphide: Electronic, vibrational and rotational structure of the A[14.79]8.5-X8.5, A[14.79]8.5-W[0.25]7.5 and A[14.79]8.5-V[0.98]7.5 transitions

Laser induced fluorescence spectra of HoS have been obtained using a Broida oven and a ring dye laser. Dispersed fluorescence spectra showed transitions from a common upper state, A[14.79]8.5 to the v = 0 and 1 vibrational levels of three low lying states, labelled X8.5, W[0.25]7.5 and V[0.98]7.5 (the states are labelled [10⁻³T₀]Ω according to their energy and Ω assignment). High resolution excitation spectra were obtained for all six transitions and a rotational analysis yielded the following principal constants, in cm⁻¹, for the X, W and V states, respectively: T₀ = 0, 251.8713(31), 980.6969(37); B_e = 0.121903(42), 0.121729(37), 0.122561(34); ΔG_1/2 = 463.8811(46), 462.9411(45), 461.2084(127). For the A state, T₀ = 14794.6987(28) cm⁻¹ and B₀ = 0.112596(29) cm⁻¹. The three low lying states are shown to arise from the Ho²⁺[4f¹⁰(⁵I₈)6s]S²⁻ configuration in accord with Ligand Field Theory predictions. The atomic origin of each of the three low lying electronic states was determined from the observed resolved hyperfine structure.     

Rotational levels of the (0 0 0) and (0 1 0) states of D2O from hot emission spectra in the 320-860 cm region

The far-infrared emission spectra of deuterated water vapour were measured at different temperatures (1370, 1520, and 1950 K) in the range 320-860 cm⁻¹ at a resolution of 0.0055 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 1150 new measured lines for the D₂¹⁶O molecule corresponding to transitions between highly excited rotational levels of the (0 0 0) and (0 1 0) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J_max=26 and for the (0 0 0) ← (0 0 0) band, J_max=25 and for the (0 1 0) ← (0 1 0) band, and J_max=26 and for the (0 1 0) ← (0 0 0) band. The estimated accuracy of the measured line positions is 0.0005 cm⁻¹. To our knowledge no experimentally measured rotational transitions for D₂¹⁶O within an excited vibrational state have been available in the literature so far. An extended set of experimental rotational energy levels for (0 0 0) and (0 1 0) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.0012 cm⁻¹ for 692 rotational levels of the (0 0 0) state and 0.0010 cm⁻¹ for 639 rotational levels of the (0 1 0) vibrational state. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surface [J. Chem. Phys. 106 (1997) 4618] for the (0 0 0) and (0 1 0) states is discussed.     

Iron isotope effect on Tc in optimally-doped (Ba,K)Fe2As2 (Tc = 38 K) and SmFeAsO1−y (Tc = 54 K) superconductors

We report the iron isotope effect on a transition temperature (T_c) in an optimally-doped (Ba,K)Fe₂As₂ (T_c = 38 K) and SmFeAsO_1−y (T_c = 54 K) superconductors. In order to obtain the reliable isotope shift in T_c, twin samples with different iron isotope mass are synthesized in the same conditions (simultaneously) under high-pressure. We have found that (Ba,K)Fe₂As₂ shows an inverse iron isotope effect α_Fe = −0.18 ± 0.03 while SmFeAsO_1−y shows a small iron isotope effect α_Fe = −0.02 ± 0.01, where the isotope exponent α is defined by T_c ∼ M^−α (M is the isotopic mass). The results show that α_Fe changes in the iron-based superconductors depending on the system. The distinct iron isotope effects imply the exotic coupling mechanism in the iron-based superconductors.     

Laser spectroscopy of the B[21.68]8-X8, B′[21.65]8-X8 and C[22.3]7-X27 transitions of holmium monofluoride

The spectrum of holmium monofluoride (HoF) in the blue (420-480 nm) region has been studied using laser-induced fluorescence. Previous work [J. Phys. B 7 (1974) L234] had assigned several bands in this region to the B8-X8 transition. By obtaining wavelength selected laser excitation spectra at high resolution and rotationally analyzing seven bands in this region, we have shown that not all the bands previously assigned to the B8-X8 system belong to the same electronic transition and have identified three separate transitions which we have labelled B8-X8, B′8-X8, and C7-X₂7. Preliminary low resolution dispersed fluorescence spectra have shown several excited states at energies greater than 4000 cm⁻¹ above the ground state and, though not all could be assigned, ligand field theory calculations are consistent with assigning them to the first excited spin-orbit component of the Ho⁺(4f¹⁰6s²)F⁻ ground state configuration or to the first excited configuration, Ho⁺(4f¹¹6s)F⁻. The results of the dispersed fluorescence experiments also tentatively place the X₂7 state at ∼70 cm⁻¹ above the ground X7 state.     

Frequency measurement of pure rotational transitions in the v2 = 1 state of H2O

Frequencies of pure rotational transitions in the v₂ = 1 vibrationally excited state of H₂¹⁶O were measured with a tunable far-infrared spectrometer in the frequency range of 0.5-5 THz. Molecular parameters of Watson’s A-reduced Hamiltonian have been obtained to reproduce the observed frequencies.     

High sensitivity ICLAS of H2O in the region of the second decade (11 520-12 810 cm)

The high resolution absorption spectrum of the H₂¹⁸O isotopologue of water has been recorded by Intracavity Laser Absorption Spectroscopy (ICLAS) with a sensitivity on the order of α_min ∼ 10⁻⁹ cm⁻¹. The 11 520-12 810 cm⁻¹ spectral region corresponding to the 3ν + δ decade of vibrational states, was explored with an ICLAS spectrometer based on a Ti:Sapphire laser. It allowed detecting transitions with an intensity down to 10⁻²⁷ cm/molecule which is about 100 times lower than the weaker line intensities available in the literature, in particular in the HITRAN database.The rovibrational assignment was performed on the basis of the results of variational calculations and allowed for assigning 3659 lines to the H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, HD¹⁶O and HD¹⁸O species, leaving only 1.7% unassigned transitions. A line list including 1712 transitions of H₂¹⁸O has been generated and assigned leading to the determination of 692 rovibrational energy levels belonging to a total of 16 vibrational states, 386 being newly observed. A deviation on the order of 25% has been evidenced for the average intensity values given by HITRAN and the results of variational calculations. Ninety two transitions of the HD¹⁸O isotopologue could also be assigned and the corresponding upper rovibrational levels are given.