The microwave and millimeter-wave spectrum of methylchloroform

The microwave and millimeter-wave spectra of methylchloroform, CH₃C³⁵Cl₃, have been reexamined in detail, including the hyperfine structure due to the three ³⁵Cl quadrupolar nuclei. Good values are found for the rotational and centrifugal distortion constants of the ground state and the lowest E state v₁₂ = 1, and values are also given for the weaker A₂ torsional state.     

The microwave spectrum of sodium tetrahydroborate NaBH4 in excited vibrational states: Coriolis interaction between the Na-BH4 stretching and the BH4 rocking vibrations

Two sets of vibrational satellites have been observed in the rotational spectrum of sodium tetrahydroborate NaBH₄, and have been assigned to the non-degenerate, Na—BH₄ stretching and the degenerate BH₄ rocking (or internal rotation) states. The observation was extended from the J = 11 ← 10 up to J = 20 ← 19 transitions. The vibrational satellites showed anomalous K structure; higher-K lines of the non-degenerate state appeared at higher frequencies, in reverse to those of the ground state, whereas the spectra in the degenerate state exhibited a K pattern similar to but somewhat more widely spread than that of the ground state. These anomalies are ascribed to the Coriolis interaction between the two excited vibrational states. The spectra observed were analysed using a C_3v symmetric-top rotational Hamiltonian, which took into account the Coriolis interaction explicitly. The A rotational constants, the energy difference δE between the two interacting vibrational states, and the first- and second-order Coriolis interaction constants have been derived.     

The rotational spectrum of 13C2HD in the ground and excited bending states

The pure rotational spectrum of ¹³C₂HD was recorded in the range 100–700 GHz. Lines belonging to the ground vibrational state were observed from J^″ = 1 to J^″ = 11. Several absorption lines were also detected in the bending states v₄ = 1 (Π), v₅ = 1 (Π), v₄ = 2 (Σ⁺ and Δ), v₅ = 2 (Σ⁺ and Δ), v₄ = v₅ = 1 (Σ^?, Σ⁺ and Δ), v₄ = 3 (Π and Φ) and v₅ = 3 (Π and Φ). The transition frequencies measured in this work were fitted together with all the infrared lines available in the literature. The global fit allowed a very accurate determination of the vibrational, rotational and ?-type interaction parameters for the bending states of this molecule.     

Rotation-vibration analysis of the microwave spectrum of cyanobutadiyne,H(CC)2CN

The detailed rotational spectrum of the linear molecule cyanobutadiyne, H(CC)₂CN, has been observed in the range 26.5 to 40.0 GHz. In particular, a study has been made of transitions belonging to the vibrationally excited states (including combination states) of the degenerate vibrations ν₁₀ and ν₁₁. Particular attention has been focused upon two series of satellites: one in which v₁₁ = 1–8 and a second in which v₁₀ = 1 while v₁₁ varies from 1–7 for a given J transition. The analysis was performed using a least-squares criterion to fit all the transitions simultaneously. In addition to providing confirmation of the forms of the vibrational and rotational l-resonance matrix elements, the analysis has demonstrated that the widely spaced l quartets observed in combination states with odd Σ_iv_i can be attributed to a strong mixing of the four l = 1 states by vibrational l resonance. It has also been found that it is only possible to determine the sign of the product of the offdiagonal parameters and not the sign of any one parameter. Therefore the reported assignment is not unique. As confirmation of the validity of the analysis, the computer simulation of the spectrum is compared with that observed.     

The microwave spectrum of BrF5 in excited vibrational states: A B1-B2 splitting of kl = 3 levels and a determination of the C rotational constant in the state v9 (E) = 1

It is shown that, in C_4v molecules, the (Δl, Δk) = (2,2) matrix elements should lead to a splitting of the normally degenerate kl = 3 levels by their different interactions with the l-doubled (q^?) kl = ?1 states. The effect is only appreciable for a restricted range of J-values. In the v₉ = 1 state of BrF₅, this occurs at J ～ 7 due to the Coriolis resonance between ν₅ and ν₉, and measurements of the resultant splitting of the kl = 3 transitions are reported for J6 → 7 and J7 → 8. An analysis of this splitting combined with earlier data for BrF₅ allows a reasonably precise determination of the rotational constant C₉. From this result, improved ground state structural parameters are derived for BrF₅ from spectroscopic data only.     

Laser spectroscopy of perturbed states of BaO in the region above 32 000 cm−1

The excitation spectrum of BaO in the region above 32 000 cm⁻¹ was investigated with a frequency-doubled pulsed dye laser. We have observed fully developed rotational structures of the C¹Σ⁺-X¹Σ⁺ transition. The analysis of the vibrational states v′ = 0 through 7 leads to a large number of perturbations. This spectroscopic information in combination with the observation and rotational analysis of transitions to several new electronic states allows a systematic summary, which gives more than eight electronic states in the investigated region. Besides the known states B, C, D and c, we find four new bound states, designated by E, F, G, and H. For all states molecular constants are given. The discussion of possible molecular electron configurations leads to classifications of the molecular electronic states. Our results on the vibrational levels v′ = 0 to 3 are in reasonable agreement to the optical-optical double resonance work of R. A. Gottscho, P. S. Weiss, and R. W. Field [J. Mol. Spectrosc. 82, 283–309 (1980)], but show several new details.     

Microwave spectrum of silyl fluoride: Coriolis resonance between ν2 and ν5 states

The J = 1 ← 0 and J = 2 ← 1 microwave rotational transitions of SiH₃F and SiD₃F have been measured for the ground and the v₂ = 1, v₃ = 1, v₅ = 1, and v₆ = 1 vibrational states, for which the various rotational and vibration-rotation interaction constants have been obtained. Both molecules show an X-Y Coriolis resonance between the ν₂ and ν₅ vibrational states, whose separation are 29 and 8 cm^?1, respectively. In the case of SiD₃F the resonance is very strong and an exact numerical diagonalization of the energy matrix was employed.     

The microwave spectrum,conformation, and vibration-rotation interaction of N-cyanopyrrolidine

The microwave spectrum of N-cyanopyrrolidine was observed and assigned in the ground and nine excited states. In the lowest two states, split 3.9 cm^?1 by a ring-puckering, nitrogen-inversion motion, the rotational constants are (for v = 0) A = 6585.05 ± 3.83, B = 1919.54 ± 0.05, C = 1583.84 ± 0.05, and (for v = 1) A = 6575.31 ± 6.01, B = 1922.37 ± 0.08, C = 1586.44 ± 0.08 MHz. Deviations from rigid rotor behavior in the lowest two states were described and analyzed by inclusion of a Hamiltonian term coupling the states via the internal vibrational angular momentum. The observed conformation of the five-membered ring system was found to be the envelope equatorial form. The tunneling motion which interconverts equivalent conformers has been discussed, and the qualitative nature of the potential energy surface has been described and compared to the parent unsubstituted molecule.     

Microwave spectrum of Trioxane in four excited degenerate vibrational states,especially in the 2ν20 (E) state and the combination state ν7 (A1) + ν20 (E)

The microwave spectra of the Trioxane molecule in the doubly excited degenerate vibrational state 2ν₂₀(E) and in the combination state ν₇(A₁) + ν₂₀(E) are reported for several J values. Molecular constants of these states have been determined. The excited states ν₂₀(E) = 1 and ν₁₉(E) = 1 previously studied by a perturbation formula have been analyzed by a direct diagonalization method of the energy matrix. Parameters which give the variation of the rotational constant B_V as a function of the quantum number v have been obtained.     

Study of the torsion-rotation Hamiltonian for symmetric tops using the millimeter wave spectrum of methyl silane

The torsion-rotation Hamiltonian for symmetric tops has been tested in methyl silane by combining recent anticrossing molecular beam measurements in the ground torsional state (v = 0) with pure rotational spectra taken for v as high as 4. The earlier microwave data set which consisted of J = 1 ← 0 and 2 ← 1 has been greatly extended by studying millimeter transitions for J = 4 ← 3, 5 ← 4, and 13 ← 12. An analysis of the 72 rotational frequencies for v ≤ 2 and the 15 anticrossing data for v = 0 yielded an excellent fit using 14 rotational, torsional, and distortion constants including the effective values for the A rotational constant and the barrier height V₃. No satisfactory fit could be obtained when the data set was extended to include measurements for (v = 3) or (v = 4). For each of these higher torsional levels, the difference between the observed frequencies and the predictions based on the best (v ≤ 2) constants can be expressed in terms of a shift δB_v in the B rotational constant, where δB_v is a smooth function of the torsional energy. This disagreement is of particular interest because it may result from the fact that the molecule passes from hindered to free rotation as v is increased from 2 to 4. The possibility of perturbation by a low-lying vibrational level is considered briefly. The information contained in the different types of spectra is discussed; the redundancy relations are treated and a Fourier expansion of the diagonal torsional matrix elements is introduced. For ¹²CH₃²⁹SiH₃, ¹²CH₃³⁰SiH₃, and ¹³CH₃²⁸SiH₃ pure rotational spectra for v = 0 were studied briefly in natural abundance. The results were combined with existing data for two deuterated symmetric rotors to obtain a structure based only on symmetric top rotational constants.     

Amino wagging and inversion in hydrazines: RR branch of the antisymmetric wagging band of NH2NH2

Infrared absorption spectrum of undeuterated hydrazine in the gaseous state has been observed with a resolving power better than 0.06 cm^?1 in the 1024 ～ 961 cm^?1 region, where the ^RR- and ^RQ-branch lines of the antisymmetric wagging band (v_a = 1 ← 0) appear. It has been found that every line belonging to the ^RR branch as well as every ^RQ peak of the band splits into four components, a, b, c, and d. This is explained by considering that the v_a = 0 state splits into A_I, E, and B₂ substates and the v_a = 1 state into B₁, E, and A₂ substates, because of the four equivalent potential minima (D₄) of the hydrazine molecule which are reached by inversions of the two amino groups. From the observed wave numbers of the ^RR lines, effective values of the rotational constants of the B₁, E, and A₂ sublevels of the v_a = 1 state were obtained. On the basis of these values and the ones for the A₁, E, and B₂ sublevels of the ground vibrational state, obtained from a previous microwave study, a discussion of the antisymmetric wagging-inversion coordinate is given.     

Analysis of the ν6 band of 12CH3D at 8.6 μm

The ν₆(E) fundamental vibration-rotation band of monodeuteromethane (¹²CH₃D) has been recorded in the spectral range 1033–1270 cm^?1 with a resolution of approximately 0.04 cm^?1. Of the 669 transitions with J′ ≤ 17 identified, 633 have been retained for the determination of the rotational levels in the upper state v₆ = 1. The Coriolis interaction between the v₆ = 1(E) and v₃ = 1 (A₁) vibrational states of ¹²CH₃D results in large A₁A₂ splittings of levels with v₆ = 1 and |K ? l₆| = 0 or 3; the mixing in K and l₆ also gives rise to some ten forbidden transitions observed in the spectra. These effects have been very well explained within the formulation based on the contact transformation method. Values of 15 molecular structure constants of the v₆ = 1 state have been determined from a least-squares analysis of the 633 retained transitions. These constants can be used to estimate values of the upper-state energies up to fourth order, and through them the spectral positions of the 633 retained transitions are reproduced with an overall standard deviation of 0.013 cm^?1, which is within experimental uncertainties.     

Treatment of the predissociation of the A1Σu+ state of As2 by the interaction with a repulsive state

The rotational analysis of the electronic spectrum of the As₂ molecule has shown a strong predissociation in the A¹Σ_u⁺ state above the v = 7 level. The resultant widths of the rotational absorption lines have been measured for the vibrational levels v = 9 to 15. The numerous experimental data allowed us to consider the predissociation state as a repulsive one according to the C⁺ predissociation case described by Mulliken. A numerical treatment based on a semiclassical method has been performed in order to obtain a good representation of the potential curve of the repulsive state near the crossing point.     

Microwave spectra of thionyl fluoride in vibrationally excited states

The microwave spectrum has been observed and rotational constants obtained for the v₄ = 1 and v₆ = 1 vibrationally excited states of thionyl fluoride. The perturbation of the C rotational constant is explained in terms of a Coriolis resonance between these levels.     

Ground state rotational energies of C3v quasi-spherical top molecules: Applications to 16OPF3 and PH3

Rotational spectra of the quasi-spherical symmetric molecules, ¹⁶OPF₃ and PH₃, are analyzed with all the data currently available. In both cases the current formulation that uses rotational contact transformations to completely diagonalize the ground state energy matrix appears to be inadequate, due to the smallness of the quantity |;A₀ ? B₀|. This quantity represents only 5% of A₀ or B₀ in the case of OPF₃ and 11% in the case of PH₃. Thus, both analyses require the resonance terms in ΔK = ±3 and/or ΔK = ±6 to be taken into account through diagonalization of the energy matrix. The ground state parameters as well as the ground state energies are given for both molecules.     

Microwave spectrum of the C4v molecule IF5 in the excited vibrational states v5(B1) = 1 and v9(E) = 1: Analysis of the ν5-ν9 Coriolis resonance

Measurements of the microwave spectrum of the C_4v molecule IF₅ in the excited vibrational states v₅(B₁) = 1 and v₉(E) = 1 are reported for the transitions J4 → 5, 5 → 6, 6 → 7, 8 → 9, and 9 → 10 (27–55 GHz). The Coriolis resonance interaction between these two states is analyzed by diagonalization of Hamiltonian matrices of dimension 3 × (2J + 1) in which all (Δl,Δk) = (±2, ±2)(q⁺), (±2, ±2)(q^?), and (0, ±4)(R₆) interactions are included as off-diagonal terms in addition to the v₅ = 1 ? v₉ = 1, l₉ = ±1(R₅₉) Coriolis interaction. In the v₉ = 1 state spectra, the $\text{B}{}_1\text{B}{}_2$l-doubling of the kl = ?1 transitions and $\text{A}{}_1\text{A}{}_2$ splittings of the kl = ?3 transitions and $\text{B}{}_1\text{B}{}_2$ splittings of the kl = +3 transitions, all enhanced by the Coriolis resonance, have been observed and measured. Least-squares refined rovibrational parameters for the v₅ = 1 and v₉ = 1 states are reported and a preliminary value for the rotational constant C₉ has been obtained.     

First- and second-order Coriolis interactions in symmetric top molecules: Application to the microwave spectrum of cyclopentadienyl thallium

Matrix elements are derived for both first- and second-order Coriolis interactions between A₁ and E₁ vibrational modes in symmetric tops, with particular reference to sign. The results are applied to the observed microwave transitions J → J + 1 for A₁ and E₁ states of the C_5ν molecule cyclopentadienyl thallium in various excited vibrational states. The microwave transitions in the excited A₁ states v₄ = 1, 2, 3, the excited E′ state v′₀ = 1 and the combination state v₄ = 1, v′₀ = 1 have yielded constants which are anomalous in several respects (1). Coriolis interactions between the ν₄ and ν₁₀ vibrations are shown to account for the observed anomalies.     

Rotational spectrum of trans-trans diethyl ether in the ground and three excited vibrational states

We report the results of a comprehensive reinvestigation of the rotational spectrum of diethyl ether based on broadband millimetre-wave spectra recently recorded at The Ohio State University and in Warsaw, covering the frequency region 108-366 GHz. The data set for the ground vibrational state of trans-trans diethyl ether has been extended to over 2000 lines and improved spectroscopic constants have been determined. Rotational spectra in the first excited vibrational states of the three lowest vibrational modes of trans-trans-diethyl ether, ν₂₀, ν₃₉, and ν₁₂ have been assigned. The v₂₀ = 1 and v₃₉ = 1 states are near 100 cm⁻¹ in vibrational term value and are coupled by a strong c-axis Coriolis interaction, which gives rise to many spectacular manifestations in the rotational spectrum. All of these effects have been successfully fitted for a dataset comprising over 3000 transitions, leading to precise determination of the energy difference between these states, (ΔE/hc)=10.400222(5) cm⁻¹. A newly developed software package for assignment and analysis of broadband spectra is described and made available.     

Matrix diagonalization treatment of l-type resonance in the rotational spectrum of trifluoroacetonitrile in the states v8 = 1 and v8 = 2

Anomalies in the microwave spectrum of CF₃CN in the state v₈ = 1 have been completely resolved by a diagonalization treatment of the matrix elements 〈l, K|l ± 2, K ± 2〉. Effects other than l-type resonance are thereby ruled out. Computation was greatly facilitated by a convenient factorization of the energy matrix which makes the method readily applicable to a large number of problems in vibration-rotation analysis. The general applicability of the method to higher vibrationally excited states was illustrated by a successful treatment of the microwave spectrum in the state v₈ = 2.     

Spectrum and energy levels of Cr3+ ions and exchange-coupled Cr3+ pairs in lanthanum aluminate

From the optical spectra the energy levels of the Cr³⁺ ion in LaAlO₃ were determined. In the cubic field approximation we obtained with the parametersDq=1750cm^-1,B=661 cm^-1, andC=2908 cm^-1 a good agreement between the calculated and measured energies. For higher Cr³⁺ concentrations the fluorescence spectrum of the exchange-coupled first nearest (1N) Cr³⁺ pairs was separated from the vibronic fluorescence spectrum of the single ions by selective excitation. From the experimental data the energy level scheme of the 1N pairs is constructed for the states ¦⁴ A ₂·⁴ A ₂〉 and ¦⁴ A ₂·² E〉. In the ground state the pairs are ordered antiferromagnetically due to an isotropic exchange interaction with an exchange integralJ=(?68 ± 1) cm^-1. From the fluorescence decay the intrinsic lifetimes of the fluorescent states of the single ions, the 1N and the 2N pairs were determined to be equal to (86± 4) msec, (1.75± 0.25) msec, and (31 ± 5) msec respectively. The fluorescence decay shows an energy transfer between the single ions and the pairs.