The second torsional state of acetic acid

We have fitted to within experimental accuracy a data set for acetic acid CH₃COOH consisting of 2103 v_t=0, 1111 v_t=1 and 634 v_t=2 microwave lines, using the so-called “rho axis method” and a model extended to include perturbation terms through eighth order. The previously published 2109 v_t=0 and 409 v_t=1 microwave lines have been extended by new measurements from Kharkov. The final fit requires only 62 parameters to achieve a unitless weighted standard deviation for the whole fit of 0.85 for a total of 3848 lines and includes transitions with J27 (15) and |K_a|13 (8) for the v_t=2 A (E)-species, respectively. This result represents a significant improvement over our previous fit which was dominated by v_t=0 transitions. A calculation of the linestrengths of torsion–rotation transitions is also provided.     

High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

On the high resolution spectroscopy and intramolecular potential function of SO2

Two weak stretching bands, ν₁ + 3ν₃ and 3ν₁ + ν₃, of the sulfur dioxide molecule have been recorded at high resolution and analyzed for the first time with using a Fourier transform Bruker IFS-120 HR interferometer. About 1000 transitions with J^max. = 51, , and 900 transitions with J^max. = 53, have been assigned to the bands ν₁ + 3ν₃ and 3ν₁ + ν₃, respectively. Analysis of the recorded spectra was made using the model of isolated vibrational states. Parameters obtained from the fit reproduce the initial experimental ro-vibrational energies with the rms deviation of 0.0006 and 0.0012 cm⁻¹ for the bands, 3ν₁ + ν₃ and ν₁ + 3ν₃, respectively. The problem of determination of the intramolecular potential function of SO₂ is discussed.     

The millimetre-wave rotational spectrum of phenylacetylene

The room-temperature rotational spectrum of phenylacetylene (C₆H₅CCH), was studied at frequencies up to 340 GHz. Extensive new measurements, covering rotational transitions with quantum number values up to J=140 and K_a=59, allowed determination of precise spectroscopic constants for the ground state and for the lowest two excited vibrational states, v₂₄=1 and v₃₆=1. The two excited states belong to the lowest B₁ and B₂ symmetry normal modes and their rotational transitions are very strongly perturbed by a-axis Coriolis resonance. A successful fit of the resonance is reported, resulting in and , in good agreement with results of ab initio computations.     

Highly excited rovibrational states of HNC

The emission spectrum of HCN has been recorded at 1463 K using hot gas molecular emission (HOTGAME) spectroscopy in the wavenumber region of 2900–3500 cm⁻¹ with a resolution of 0.01 cm⁻¹. The dense emission spectrum was analyzed with the spectrum analysis software SyMath™ implemented in the Mathematica™ computer algebra system. This work reports the analysis of the band series up to v₂ = 8 and of the band series up to v₂ = 6.36 rovibronic (v₁, v₂, l, e/f, v₃) substates of HCN including all l = 0, 2, 4, 6, 8 sublevels of the highly excited bending combination mode have been characterized for the first time and for the 22 known vibrational sublevels it was possible to improve the existing spectroscopic constants substantially. 18 (v₁, v₂, l, v₃) vibrational sublevels are located for the first time relative to the 00⁰0 state. The analysis reported here includes rovibrational states up to very large rotational excitations of J = 60–80. For the combination states the rotational states have been determined up to J = 86 which corresponds to 7000 cm⁻¹ rotational excitation energy, this state is only 2000 cm⁻¹ below the isomerization barrier. It was possible to determine for the first time the L_v high order rotational constant for many states reported in this work.     

High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands

We report a rovibrational analysis of the ν₄ and ν₆ fundamentals and the 2ν₅ overtone of HNSO from high-resolution Fourier transform infrared spectra. The ν₆ band (out-of-plane bend) centred at 757.5 cm⁻¹ is c-type. The ν₄ band (HNS bend) centred at 905.9 cm⁻¹ is predominantly a-type with a very weak b-type component (). Numerous global perturbations and localized avoided crossings affecting the v₄ = 1 rotational levels were successfully treated by inclusion of Fermi and c-axis Coriolis resonance terms between v₄ = 1 and v₅ = 2, and a b-axis Coriolis resonance term between v₄ = 1 and v₆ = 1. The latter term gives rise to an avoided crossing with an extraordinary ΔK_a = 5 selection rule. The Fermi resonance between v₄ = 1 and v₅ = 2 gives rise to strong mixing of their rotational wavefunctions in the vicinity of K_a = 18. The resultant borrowing of intensity made it possible for 2ν₅ transitions in the range K_a = 16–19 to be assigned and included in a global rovibrational treatment of all three band systems.     

The ground and first excited torsional states of methyl carbamate

A global fit within experimental accuracy of microwave and millimeter-wave transitions in the ground and first excited torsional states of methyl carbamate (H₂NC(O)OCH₃) is presented. The data set consisting of 995 v_t = 0 and 731 v_t = 1 transition frequencies combines 1544 new measurements from Kharkov with previously published v_t = 0 microwave lines. In this study the so-called “rho axis method” that treats simultaneously both A and E species of the ground and first excited torsional states is applied to the methyl carbamate data set for the first time. The final fit requires only 32 parameters to achieve a unitless weighted standard deviation for the whole fit of 0.89 for a total of 1726 transitions with rotational quantum numbers up to J ? 20 and K_a ? 10. The barrier to internal rotation of the methyl group obtained in this study, V₃ = 359.141(24) cm⁻¹, is in good agreement with previously published values but more accurate.     

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.     

High-resolution FTIR and MMW study of the v4 = 2 (A1, E) excited state of NF3 near 985 cm: the axial ground state rotational constants derived by the “loop-method”

The two substates v₄ = 2⁰ (A₁, 983.702 cm⁻¹) and v₄ = 2^±2 (E, 986.622 cm⁻¹) of the oblate symmetric top molecule, ¹⁴NF₃, have been studied by high-resolution (2.5 × 10⁻³ cm⁻¹) infrared spectroscopy of the overtones and 2ν₄ − ν₄ hot bands. Transitions of the overtone, the hot band, and the previously measured fundamental band were combined to yield 585 ground state combination differences differing in K by ±3, with K_max = 36. Using the “loop-method,” a fit (standard deviation σ = 0.320 × 10⁻³ cm⁻¹) provided a complete set of the hitherto not experimentally known axial ground state constants. In units of cm⁻¹ these have the following values: . Upper state parameters were determined using a vibrationally isolated model. Considering l (2, 2) and l (2, −1) interactions between the v₄ = 2⁰ and v₄ = 2^±2 substates and effects accounting for the l (4, −2) interactions within the kl = −2 levels, 25 upper state parameters were obtained by fitting 2747 IR data (1842 transitions, 905 deduced energies, J_max = 42, K_max = 39) with σ_IR = 0.353 × 10⁻³ cm⁻¹. Moreover, millimeter-wave spectroscopy furnished 86 transitions (J_max = 16, K_max = 13) measured on the v₄ = 2 excited state. A merged fit, refining 24 parameters using the described model gave σ_IR = 0.365 × 10⁻³ cm⁻¹ andσ_MMW = 0.855 × 10⁻⁶ cm⁻¹ (26 kHz). The anharmonicity constants (in cm⁻¹) are x₄₄ = −0.84174 (2) and g₄₄ =  + 0.73014 (1). In addition to this model, the D, Q, and L reductions of the rovibrational Hamiltonian were tested. Standard deviations σ_IR = 0.375 × 10⁻³ cm⁻¹ and σ_MMW = 0.865 × 10⁻⁶ cm⁻¹ were obtained for both D and L reductions, and σ_IR = 0.392 × 10⁻³ cm⁻¹ and σ_MMW = 0.935 × 10⁻⁶ cm⁻¹ for Q reduction. The unitary equivalence of the majority of the 18 tested relations between the derived parameters was satisfactorily fulfilled. This confirms that the v₄ = 2 excited vibrational state can be considered in reasonable approximation to be isolated.     

Quantitative analysis of Earth’s field NMR spectra of strongly-coupled heteronuclear systems

In the Earth’s magnetic field, it is possible to observe spin systems consisting of unlike spins that exhibit strongly coupled second-order NMR spectra. Such spectra result when the J-coupling between two unlike spins is of the same order of magnitude as the difference in their Larmor precession frequencies. Although the analysis of second-order spectra involving only spin-½ nuclei has been discussed since the early days of NMR spectroscopy, NMR spectra involving spin-½ nuclei and quadrupolar (I > ½) nuclei have rarely been treated. Two examples are presented here, the tetrahydroborate anion, , and the ammonium cation, . For the tetrahydroborate anion, ¹J(¹¹B,¹H) = 80.9 Hz, and in an Earth’s field of 53.3 μT, ν(¹H) = 2269 Hz and ν(¹¹B) = 728 Hz. The ¹H NMR spectra exhibit features that both first- and second-order perturbation theory are unable to reproduce. On the other hand, second-order perturbation theory adequately describes ¹H NMR spectra of the ammonium anion, , where ¹J(¹⁴N,¹H) = 52.75 Hz when ν(¹H) = 2269 Hz and ν(¹⁴N) = 164 Hz. Contrary to an early report, we find that the ¹H NMR spectra are independent of the sign of ¹J(¹⁴N,¹H). Exact analysis of two-spin systems consisting of quadrupolar nuclei and spin-½ nuclei are also discussed.     

New observation of the , 1Δg, and 2Πg states and molecular constants with all Li2, Li2, and LiLi data

This paper reports our new observation of the , 1³Δ_g (v = 2–4), and 2³Π_g (v = 2–8) states of ⁶Li⁷Li by continuous wave perturbation facilitated optical–optical double resonance spectroscopy. Combining our new experimental term values of ⁶Li⁷Li with the available experimental data of ⁶Li₂ and ⁷Li₂, molecular constants and potential energy curves by Rydberg–Klein–Rees and direct-potential-fit techniques have been determined. Born-Oppenheimer breakdown parameters of the Li₂ 1³Δ_g and 2³Π_g states are calculated.     

Effect of In-content on the optical properties of a-Se films

The optical transmission spectra of amorphous (a-) Se_1−xIn_x films, with x = 0.0, 0.05, 0.18 and 0.35, that prepared by thermal evaporation from their corresponding bulk ingots, are recorded over the spectral region of 500–2500 nm. A simple straight forward procedure proposed by Swanepeol has been applied to determine the two components of the complex refractive index (). The dispersion of is examined in terms of the Wemple and DiDomenico model and is discussed in terms of In-content. An estimation of various optical parameters such as, the optical energy gap (E_g = 1.96–1.33 eV), single oscillator energy (E_o = 3.95–3.16 eV), oscillator dispersion energy (E_d = 22.6–31.6 eV), lattice oscillator strength (E_l = 0.38–0.61 eV) and wavelength at zero material dispersion (λ_c = 2.0569–2.0879 μm) have been given and discussed in relation to the coordination number, hydrostatic density and formed chemical bonds that are introduced in the network of a-Se with the introduction of up to 35 at.% In.     

A new joint analysis of the ground and first excited torsional states of methylformate

A global fit within experimental accuracy of microwave rotational transitions in the ground and first excited torsional states (v_t = 0 and 1) of methylformate (HCOOCH₃) is reported, which combines older measurements from the literature with new measurements from Kharkov. In this study the so-called ‘‘rho axis method’’ that treats simultaneously both A and E species of the ground and first excited torsional states is used. The final fit requires 55 parameters to achieve an overall unitless weighted standard deviation of 0.71 for a total of 10533 transitions (corresponding to 9298 measured lines) with rotational quantum numbers up to J ? 62 and K_a ? 26 in the ground state and J ? 35 and K_a ? 23 in the first excited torsional state. These results represent a significant improvement over past fitting attempts, providing for the first time a fit within experimental accuracy of both ground and first excited torsional states.     

High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

The 2ν4 overtone bands of FClO3

The high resolution infrared spectrum of the mono-isotopic species F³⁵Cl¹⁶O₃ has been studied in the region of the 2ν₄ overtone, from 2560 to 2680 cm⁻¹. The perpendicular component is strong and clearly observed while the parallel component is very weak and almost completely hidden by the perpendicular one. Their origins differ by 12.6 cm⁻¹, the being located at higher wavenumbers. The band is perturbed by the anharmonic interaction between the v₄ = 2, l₄ = ?2 and v₂ = v₄ = v₅ = 1, l₄ = l₅ = ±1 excited states, both of E symmetry. In total 3157 transitions have been assigned, 83% of these to , 12% to , and 5% to . The three bands have been analyzed simultaneously, taking into account the Fermi resonance effective between the excited states of E symmetry. The ro-vibration parameters of the excited states have been obtained, including the deperturbed band origins of and , at 2628.5890(4) and 2619.3342(5) cm⁻¹, respectively. The W₂₄₅ anharmonic constant is equal to 4.0161(4) cm⁻¹. The x₄₄+g₄₄ and x₂₄+x₄₅+g₄₅ anharmonicity constants have been derived from the obtained band origins and those of ν₄ and ν₂ + ν₅.     

Far-infrared laser stark spectroscopy of CH3OH and13CH3OH

The high resolution laser Stark spectra of methanol and¹³C-substituted methanol have been studied up to Stark fields of about 60 000V/cm with the HCN and DCN lasers. Numerous families of absorption lines have been observed in both parallel and perpendicular polarizations. For methanol, the transitions J _k =7₅ 6₄ A, _t=0; J _k =11₄ 10₃ E _l , _t=0; and J _k =17₃ 16₂ E₂, _t=0 have been identified while the assignments for¹³C-substituted methanol are J _k =14₈ 15₇ A, _t=0; J _k =15₃ 14₂ A⁺, _t=0; J _k =10₇ 9₆ A, _t=0; and J _k =27₉ 27₈ E₁, _t=0. Zero-field frequencies for the assigned transitions are given with improved accuracy over those calculated from available molecular constants, especially for¹³CH₃OH.     

High-resolution infrared study of the 2ν3 (A1, E) and ν1 + ν3 (E) bands of NF3

The 2ν₃ overtone (A₁, E) and the ν₁ + ν₃ (E) combination bands of the oblate symmetric top ¹⁴NF₃ were studied by FTIR spectroscopy with a resolution of 2.5 × 10⁻³ cm⁻¹. Nearly 500 lines up to K_max/J_max = 30/43 were observed for the weak A₁ component reaching the v₃ = 2⁰ substate (1803.1302 cm⁻¹), the majority of which corresponded to reinforced K = 3p-type transitions. For the strong E component reaching the v₃ = 2^±2 substate (1810.4239 cm⁻¹), about 3550 transitions were assigned up to K_max/J_max = 65/69, favoring a clear observation of the ℓ(4, −2) and ℓ(4, 4) splittings within the kℓ = −2 and +4 sublevels, respectively. The two v₃ = 2 substates are linked by the ℓ(2, 2)- and ℓ(2, −1)-type interactions, providing severe crossings, respectively, at K′ = 6 and near K′ = 24 on the v₃ = 2⁺² side. A model working in the D-reduction and including all these ℓ-type interactions could reproduce together 3695 nonzero weighted experimental data (NZW) through 33 free parameters with a standard deviation of σ = 0.357 × 10⁻³  cm⁻¹. As for the ν₁ + ν₃ (E) combination band, about 3690 lines were assigned up to K_max/J_max = 45/55. Its v₁ = v₃ = 1 upper state (1931.577 5 cm⁻¹) was treated using the same model recently applied to the v₃ = 1 (E, 907.5413 cm⁻¹) state. It yielded 21 free parameters through 3282 NZW experimental data, adjusted with σ = 0.344 × 10⁻³  cm⁻¹ in the D-reduction. For the two excited states, the small and unobserved ℓ(0, 6) interaction was tested as useless. To confirm the adequacy of the vibrationally isolated models used, some other reductions of the Hamiltonian were tried. For the v₃ = 2 state, the D-, L-, and LD-reductions led to similar σ’s, while the Q one was not successful. For the v₁ = v₃ = 1 state, the D- and Q-reductions gave comparable σ’s, while the QD-reduction was not as good. The corresponding unitary equivalence relations are generally more nicely fulfilled for the v₃ = 2 state than for the v₁ = v₃ = 1 state. The three derivable anharmonicity constants in cm⁻¹ are x₃₃ = −4.1528, g₃₃ = +1.8235 and x₁₃ = −7.9652.     

High-resolution infrared and subterahertz spectroscopy of the v2 = 1, v5 = 1, and v3 = 2 levels of CH3Cl

High-resolution Fourier-transform infrared spectra between 1235 and 1680 cm⁻¹ and subterahertz spectra between 250 and 630 GHz of monoisotopic ¹³CH₃³⁵Cl have been recorded and analyzed simultaneously, with all Coriolis, α-resonance, and l-type interactions in the polyad of the v₂ = 1, v₅ = 1, and v₃ = 2 levels taken into account. Several α-resonances (Δk = ±2, Δl = ?1) generating perturbation-allowed transitions have been assigned in the rovibrational spectra. These resonances enabled us to determine accurately and independently the ground state rotational and centrifugal distortion parameters A₀ = 5.205 746 9 (55) cm⁻¹ and . Even , which is, however, correlated to higher-order α-resonance terms, was determined. With 51 upper state parameters varied, about 5800 rovibrational wavenumbers and more than 550 rotational frequencies pertaining to the excited vibrational states were fitted within their experimental accuracy.