Rotation spectrum and infrared fundamental bands of 123SbD3. Determination of molecular geometry and ab initio calculations of spectroscopic parameters

The high resolution infrared spectrum of ¹²³SbD₃ has been recorded in the 20–350?cm^?1 range and in the regions of the ν₁, ν₃ and ν₂, ν₄ fundamental bands centred at 1350 and 600?cm^?1, respectively. Splitting of the K′′?=?3, 6 lines have been observed both in the rotation and ro-vibration spectra. A large number of ‘perturbation allowed‘ transitions with selection rules Δ(k??l) =?±?3,?±?6, and?±?9 have been identified in all fundamental bands. Accurate ground state molecular parameters have been determined by means of a simultaneous fit of the rotational transitions and about 12?000 ground state combination differences from the infrared bands. The A and B reductions of the rotational Hamiltonian provided almost equivalent results. The molecular parameters of the ν _i ?=?1 (i?=?1???4) states were obtained as a result of the simultaneous analysis of the ν₁ (A₁)/ν₃ (E) stretching and of the ν₂ (A₁)/ν₄ (E) bending dyads. In fact, the corresponding excited states are affected by strong perturbations due to rovibrational interactions of Coriolis and k-type that have been treated explicitly in the model adopted for the analysis. Improved effective ground state and equilibrium geometries were determined for the molecule and compared to those of ¹²³SbH₃. Ab initio calculations at the coupled cluster CCSD(T) level with an energy-consistent large-core pseudopotential and large basis sets were carried out to determine the equilibrium structure, the anharmonic force field, and the associated spectroscopic constants of ¹²³SbH₃ and ¹²³SbD₃. The theoretical results are in good agreement with the experimental data.     

Observation of forbidden transitions in the ν4 band of NH3: corrections to the ground state ΔK = 3 intervals

This paper presents a preliminary evaluation of the C rotational constant and coefficients of the operators P_z ²ⁿ up to n = 4 for NH₃ in the ground state. These constants are evaluated on the basis of the determination of 14 different ΔK = 3 ground state intervals obtained from measurement of many Δ(K - l) = 3 transitions observed in the ν₄ vibration rotation band. Corrections to the ground state term values for NH₃ are given as a function of K, thus permitting ΔK = 3 transitions to be determined with accuracies comparable to those of normal allowed transitions. The perturbation which gives rise to the observed transitions is large, but has not been treated in previous analyses of the ν₄-2ν₂ bands.     

Far infrared spectrum and spectroscopic constants of AsH3 in the ground state

The far ir spectrum of arsine, AsH₃, was recorded in the range 25–100 cm^?1 with a resolution of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0 rotational transitions were measured and assigned up to J″ = 12. These transitions, together with the presently available microwave and submillimeter-wave data and ground state combination differences, were analyzed on the basis of a rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The derived ground state molecular parameters reproduced the transition frequencies of both allowed and “perturbation allowed” transitions within the accuracy of the measurements. The equilibrium structure was determined for the AsH₃ molecule.     

High resolution FTIR spectra and analysis of the ν11 fundamental and of the ν2 + ν11, ν5 + ν12 and ν7 + ν16 combination bands of 12C6D6

We report results from measurements of the high resolution FTIR spectrum for the fully deuterated benzene molecule C₆D₆ in the range 450–3500 cm^?1. Accurate spectroscopic constants have been obtained for the fundamental vibration ν₁₁ at 496.208 cm^?1 and improved ground state constants have been deduced from a fit of ground state combination differences. The J structure of the combination parallel bands ν₂ + ν₁₁ (at 2798.1 cm^?1), ν₅ + ν₁₂ (1802.5 cm_?1) and ν₇, + ν₁₆ (2619.3 cm^?1) of C₆D₆ has been analysed as well, from which improved values of the band origin and of the B and D _j constants of the excited states have been obtained. The strongest hot bands accompanying these parallel transitions have been assigned by means of the anharmonic force field calculated by Maslen et al. [1992, J. chem. Phys., 97, 4233]. In particular (ν₁₁ + ν₁₆) ? ν₁₆ is assigned to the band at 492.4 cm^?1 even though its shape is typical of a perpendicular transition (PAPE). New values for the ν₅, ν₁₂ and ν₁₆ band origins are determined from the band origins of combination bands and from calculated anharmonic constants. Numerous anharmonic constants are derived from the assignment of hot band and combination transitions.     

High-resolution rotational spectroscopy of iminosilylene,HNSi

By means of Fourier transform microwave spectroscopy of a supersonic beam, the fundamental rotational transition of isotopic and vibrationally excited iminosilylene, HNSi, has been detected. In addition to seven isotopic species, vibrational satellite transitions from more than 30 vibrationally excited states, including the three fundamental modes, have been detected. Those from ν₂ are particularly intense, enabling detection of transitions from as high as (0,22⁰,0) (i.e. ～10,000 cm^?1 above ground). At high spectral resolution, well-resolved nitrogen quadrupole structure has been observed in nearly every transition. Excitation of ν₁ or ν₃ changes eQq(N) little, but eQq(N) systematically decreases with increasing excitation of the ν₂ bend, from a value of 0.376(5) MHz for (0,0⁰,0) to ?2.257(5) MHz for (0,20⁰,0). With the large amount of new data in hand, it has also been possible to determine the leading vibration–rotation constants (α_i and γ_i) for ν₂ or ν₃ to high precision, and derive a revised semi-empirical equilibrium structure for this fundamental triatomic molecule. Various electronic and molecular properties of iminosilylene have been calculated at the coupled cluster level of theory, and these generally agree well with experiment and previous calculations. An unsuccessful search for HSiN, a highly polar isomer calculated to lie nearly 3 eV above HNSi, is also reported.     

Precision infrared spectroscopy in CF379Br by means of infrared-microwave double resonance

From the observation of double resonance effects on the microwave spectrum two coincidences between 9.4 μm CO₂ laser lines and infrared transitions of the ν₆ → (ν₆ + ν₁) band of CF₃⁷⁹Br have been determined: R(30) laser line coincident with ^qR₂(7), F = 17/2→17/2 transition, R(28) laser line coincident with all four ΔF = 0 hyperfine components of the ^qQ₈(13) transition. In both cases other infrared transitions lay within the tuning range of the laser. The frequencies of these two laser lines allowed calculations of the band center frequency ν₀ = 1083.530 ± 0.001cm^?1 and α_A = 11.93 ± 0.3MHz, for the ν₆ → (ν₆ + ν₁) band.α_B constants were determined for the vibrational states v₆, (v₆ + v₁), v₁, and v₃.     

The Δk = ±2 perturbation-allowed ν4 band and inversion-rotation energy levels of 15NH3

More than 800 Δk = ±2 and 60 Δk = ±3 forbidden transitions to the ν₄ and 2ν₂ vibrational levels, respectively, have been assigned in the Fourier transform spectra of ¹⁵NH₃, recorded with a pathlength of 96 m. Combination differences derived from these transitions provide information on the spacing between the ground state energy levels with different rotational quantum numbers K in the interval from 0 to 16. These data along with wavenumbers of all the available allowed transitions pertaining to the ground and ν₂ states have been subjected to a simultaneous least-squares analysis using two different parametrization models to obtain precise values of the inversion-rotation energy levels.     

Millimeter-wave spectrum of the C4v molecule iodine oxygen pentafluoride IOF5: K-doubling of the |k| = 2 transitions in the ground state spectrum

Measurements are reported for the rotational spectrum of the C_4v molecule IOF₅ in the ground vibrational state in the range 30–75 GHz (J7 ← 6 to J17 ← 16). The K-doubling of |k| = 2 transitions due to an off-diagonal centrifugal distortion interaction of the type (Δl, Δk) = (0, ±4) has been observed. The centrifugal distortion constants D_J, D_JK, and R₆ have been determined as 0.139(2) kHz, 0.107(4) kHz, and 21(2) Hz, respectively.     

Simultaneous analysis of the microwave and infrared spectra of 14ND3 and 15ND3 for the ν2 excited state

The data on the inversion spectrum in the ν₂ state of ¹⁴ND₃ [F. Scappini, A. Guarnieri, and G. DiLonardo, J. Mol. Spectrosc.95, 20–29 (1982)] have been extended by measuring frequencies of 25 new transitions. A simultaneous least-squares analysis of these data with the ground state microwave transition frequencies and the diode laser measurements of the ν₂ band has been carried out. Improved sets of molecular parameters have been obtained for ¹⁴ND₃ and ¹⁵ND₃, including the ground and ν₂ state inversion splittings, ν₂ band origins, rotational and centrifugal distortion constants, and the parameters of the Δk = ±3n vibrational-rotational interactions.     

Line Positions and Intensities of the ν1+ ν2+ 3ν3, ν2+ 4ν3, and 3ν1+ 2ν2Bands of Ozone

Using a Fourier transform spectrometer, we have recorded the spectra of ozone in the region of 4600 cm⁻¹, with a resolution of 0.008 cm⁻¹. The strongest absorption in this region is due to the ν₁+ ν₂+ 3ν₃band which is in Coriolis interaction with the ν₂+ 4ν₃band. We have been able to assign more than 1700 transitions for these two bands. To correctly reproduce the calculation of energy levels, it has been necessary to introduce the (320) state which strongly perturbs the (113) and (014) states through Coriolis- and Fermi-type resonances. Seventy transitions of the 3ν₁+ 2ν₂band have also been observed. The final fit on 926 energy levels withJ_max= 50 andK_max= 16 gives rms = 3.1 × 10⁻³cm⁻¹and provides a satisfactory agreement of calculated and observed upper levels for most of the transitions. The following values for band centers are derived: ν₀(ν₁+ ν₂+ 3ν₃) = 4658.950 cm⁻¹, ν₀(3ν₁+ 2ν₂) = 4643.821 cm⁻¹, and ν₀(ν₂+ 4ν₃) = 4632.888 cm⁻¹. Line intensities have been measured and fitted, leading to the determination of transition moment parameters for the two bands ν₁+ ν₂+ 3ν₃and ν₂+ 4ν₃. Using these parameters we have obtained the following estimations for the integrated band intensities,S_V(ν₁+ ν₂+ 3ν₃) = 8.84 × 10⁻²²,S_V(ν₂+ 4ν₃) = 1.70 × 10⁻²², andS_V(3ν₁+ 2ν₂) = 0.49 × 10⁻²²cm⁻¹/molecule cm⁻²at 296 K, which correspond to a cutoff of 10⁻²⁶cm⁻¹/molecule cm⁻².     

High resolution diode laser measurements on the ν2 bands of 14NH3 and 15NH31

More than 500 lines in the ν₂ bands of ¹⁴NH₃ and ¹⁵NH₃ have been measured in the region 740–1200 cm^?1 with a diode laser spectrometer, with an accuracy better than 0.0005 cm^?1 for most of the lines. Wavenumbers (in cm^?1) were determined using a 3-in. Ge etalon for calibration and OCS, N₂O, NH₃, and CO₂ lines as references. The diode laser data were combined with pure inversion and inversion rotation frequencies and sets of rotational constants were obtained by the method of merged least squares. Perturbations between the Δk = ±3 levels have been taken into account in these calculations.     

Zerfallende Zustände als physikalisch nichtisolierbare Teilsysteme

Presently the investigations of decaying quantum mechanical systems lack a well-founded concept, which is reflected by several formal difficulties of the corresponding mathematical treatment. In order to clarify in some respect the situation, we investigate, within the framework of nonrelativistic quantum mechanics, the resonant scattering of an initially well localized partial wave packet ϕ_l(r, t). If the potential decreases sufficiently fast for r → ∞, ϕ_l(r, t) can be expressed at sufficiently long time after the scattering has taken place, as ϕ_l(r, t) = I(r, t) + ∑ N_iϕl(K_i, r) exp {–iK_i² t/2M} × Θ(k_i – γ_i – Mr/t), ϕ_l(K_i, r) being the resonant solution with complex “momentum” K_i = k_i – iγ_i. From this heuristic relation one can deduce not only the probability for the creation of unstable particles but also obtain some hints to a connection between decaying states and physically nonisolable partial systems. On the other hand, this connection can perhaps display the inadequacy of attempts which suggest to solve the problem of decaying states within the usual Hilbert space methods.     

High resolution FTIR study of the ν5 and ν6 bands of CH2D35Cl: analysis of resonances and determination of ground and upper state constants

The isotopically pure form of methyl chloride, CH₂D³⁵Cl, was synthesized and investigated by Fourier transform infrared spectroscopy with an unapodized resolution of 0.004?cm^?1 in the range 650–900?cm^?1, the region of the lowest fundamentals ν₅ (827?cm^?1) and ν₆ (714?cm^?1). These distinct bands have been analysed in detail in the P-, Q- and R-branches. In spite of their expected a/b-hybrid nature, both envelopes show the peculiar characteristic of only a-type bands of near prolate asymmetric top molecules. Ground state parameters have been determined for the first time through ground state combination differences from both bands. Parameters of the excited vibrational states and coupling constants have been obtained using a model which accounts for c-type Coriolis interaction and ΔK_a?=?±?2 anharmonic resonance.     

The far-infrared spectrum and spectroscopic parameters of PH3 in the ground state

The far-infrared spectrum of phosphine, PH₃, was recorded in the region between 30 and 200 cm⁻¹ at a resolution of 0.002 cm⁻¹. ΔJ = +1, ΔK = 0 rotational transitions in the ground state were measured and assigned up to J″ = 22 and K = 19. These transitions were analyzed together with the presently available microwave and submillimeter-wave data on the basis of different formulations of the rotational Hamiltonian, which included Δk = ±3 and/or Δk = ±6 interaction terms. An upper limit for the constant of the inversion splitting was obtained by fitting the same transitions to an appropriate inversion-rotational Hamiltonian. Rotational transitions in the v₂ = 1 and v₄ = 1 vibrational states were also observed.     

The v 1 and v 3 bands of ND3

High resolution (0.004cm^-1 instrumental bandwidth) interferometric Fourier transform infrared spectra of ¹⁴ND₃ were obtained on a BOMEM DA002 spectrometer under essentially Doppler limited conditions. An analysis is reported of the ND₃ stretching fundamentals with band centres at [EQUATION]₁ ⁰ (s ← a) = (2420.056 ± 0.001)cm^?1, [EQUATION]₁ ⁰(a ← s) = (2420.650 ± 0.001)cm^?1, [EQUATION]₃ ⁰(a ← a) = (2563.8840 ± 0:0005)cm^?1 and [EQUATION]₃ ⁰ (s ← s) = (2563.9161 ± 0.0005)cm^?1, with inversion tunnelling splittings Δ[EQUATION]₁ = 0.5412cm^?1 and Δ[EQUATION]₃ = 0.0209cm^?1 in the vibrationally excited levels. About 50 parameters of the effective Hamiltonian for this band system could be determined accurately. Assignments were established with certainty by means of ground state combination differences. The results are important for and are discussed in relation to the mode selective inhibition and promotion of inversion at the nitrogen atom by exciting ND stretching vibrations, and treatments of isotope e? ects on inversion of ammonia by means of effective Hamiltonians and true molecular Hamiltonians on high dimensional potential hypersurfaces.     

Analysis of the microwave spectrum of hydrazine

Microwave measurements in the interval from 6 to 133 GHz, consisting of 444 rotational transitions in the vibrational ground state of hydrazine with J ≤ 31 and K_a ≤ 6 were fit to an effective rotational Hamiltonian containing 9 asymmetric rotor constants, 14 NH₂ inversion parameters, and 1 internal rotation parameter, with an overall standard deviation of the fit of 0.40 MHz. This set of parameters contains: (i) the three rotational constants; (ii) tunneling splitting constants for NH₂ inversion at one end of the molecule, for NH₂ inversion at both ends of the molecule, and for internal rotation through the trans barrier; (iii) two K-type doubling constants affecting the K = 1 levels; (iv) an a-type Coriolis interaction with matrix elements linear in K; and (v) various centrifugal distortion corrections to the above parameters. A consistent group theoretical formalism was used to label the energy levels and to select terms in the phenomenological rotational Hamiltonian. The Hamiltonian matrix, which is set up in a tunneling basis set, is of dimension 16×16 and contains only ΔK_a = 0 matrix elements, asymmetric rotor effects being taken into account on the diagonal by terms from a Polo expansion in bⁿ. Hyperfine splittings and barrier heights are not discussed.     

The microwave spectrum of 14NH3 in the v = 000011 state

The frequencies and assignments of 50 lines in the pure inversion spectrum of ¹⁴NH₃ in the 0001¹ vibrational state are reported in the microwave frequency region 18–53 GHz and in selected regions up to 58 GHz.The J = 0 inversion frequency, K-type doubling constant K, l = 2, ?1 and molecular dipole moment in this state are 32 904.7 ± 2.0 MHz, 1.958 ± 0.040 MHz and 1.459 ± 0.002 D, respectively, where model inadequacies are included in the uncertainties of the first two parameters. The dipole moment measurements for this and the ground state are in excellent agreement with Stark laser measurements. An expression containing the effective l-type doubling constant is obtained from the combination of frequencies $\text{[ν(1, 1, 1) ? ν(1, 1, ?1) ? ν(2, 1, 1) + ν(2, 1, ?1)]}\text{8}\text{= 10 361.894 ± 0.004}\text{MHz}$. A preliminary value for the l-type doubling constant is 10 655 ± 20 MHz.     

A frequency analysis of the ν9 band of CD3CD3: experiment and ab initio calculations

The infrared gaseous spectrum of CD₃CD₃ has been measured in the range of 530–670cm^?1 to investigate vibration—torsion effects in the ν₉ band. Three separate spectra all taken under different experimental conditions were recorded. The lines with (ΔK = ?1) and with high values of K show torsional splittings that are substantially larger than expected from the observed barrier height. These splittings are caused primarily by Coriolis-type interactions between the torsional stack of ν₉ = 1 and the corresponding stack for the ground vibrational state. Because of a near-degeneracy that exists between the states (ν₉ = 0, ν₄ = 3) and (ν₉ = 1, ν₄ = 0), three subbands (K, σ) = (15,1), (16,2), (17,3) are resonantly perturbed. For these cases, perturbation-allowed 3ν₄ torsional transitions have been identified. Here σ= 0, 1, 2 or 3 labels the torsional sublevels. Measurements from the ν₉ and 3ν₄ bands, frequencies from the far-infrared torsional spectra in the ground vibrational state, and lower state combination differences from the ν₉ + ν₄ ? ν₄ band were fitted to within experimental uncertainty using an effective Hamiltonian which considered three torsional stacks; one for the ground vibrational state and two for ν₉ = 1. In all, 22 parameters were determined using a total of 2001 lines. Of these, three parameters were the interstack couplings, eight are from the ground vibrational state and 11 are from the excited vibrational state. Two barrier-dependent torsion—rotation parameters, which were essential for obtaining a satisfactory fit, were calculated by ab initio methods.     

High-resolution FTIR spectroscopy of HCFC-31 in the 950−1160 cm−1 region: rovibrational analysis and resonances in the ν4, ν9 and ν5+ν6 bands of CH235ClF

The FTIR spectrum of CH₂ClF (natural isotopic mixture) was investigated in the ν₄, ν₉ and ν₅+ν₆ band region between 950 and 1160 cm^?1 at the resolution of 0.004 cm^?1. The ν₄ and ν₅+ν₆ vibrations of A′ symmetry give rise to a/b hybrid bands with a predominant a-type component. The ν₉ vibration of A^″ symmetry, expected with a c-type band contour, shows an intense Coriolis-induced parallel component (ΔK_a = 0, ΔK_c = 0) derived from mixing with the v₄ = 1 vibrational state. The high-resolution spectra of ν₉ and ν₅+ν₆ have been analyzed for the first time, while the assignments of the ν₄ band, previously investigated, have been extended to higher J and K_a values in the b-type component. The spectral analysis resulted in the identification of 1508, 809 and 349 transitions for the ν₄, ν₉ and ν₅+ν₆ bands of CH₂³⁵ClF, respectively. Besides the strong first-order a- and b-type Coriolis resonances between ν₄ and ν₉, the ν₅+ν₆ vibration was found to interact through a c-type Coriolis with the ν₄ and 3ν₆. High-order anharmonic resonance (ΔK_a = ±2) between ν₄ and ν₅+ν₆ was also established. All the assigned data were simultaneously fitted using the Watson's A-reduction Hamiltonian in the I^r representation and the relevant perturbation operators. The model employed includes five types of resonances within the tetrad ν₄/ν₉/ν₅+ν₆/3ν₆. Α set of spectroscopic constants for ν₄, ν₉ and ν₅+ν₆ bands as well as parameters for the dark state 3ν₆ and seven coupling terms have been determined. The simulations performed in different spectral regions satisfactorily reproduce the experimental data.