The torsional spectrum of chlorine nitrate

The far-infrared torsional spectrum of ClONO₂ (chlorine nitrate) was reexamined at 0.06-cm^?1 apodized resolution. The torsional spectrum consists of a single, regularly spaced series of Q branches at 122.56 ? 2.422 v′ + 0.0296 v′² cm^?1. Chlorine nitrate is planar with torsional potential constants V₂ = 1900 ± 100 cm^?1 and V₄ = 90 ± 50 cm^?1. The torsional partition function is calculated at room and stratospheric temperatures.     

The ring puckering vibration of trimethylene sulfoxide: Far-infrared spectrum from 50 to 675 cm−1

A number of absorptions between 100 and 300 cm^?1 in the infrared spectrum of trimethylene sulfoxide vapor have been observed and assigned to Δv_p = 1 and 2 transitions in the ring puckering mode. With the aid of a computer program providing for a potential function essentially of the form V(x) = V₂x² + V₃x³ + V₄x⁴ (x the dimensioned puckering coordinate), the barrier to inversion between the stable equatorial and a possible axial conformer is established to be 1205 cm^?1 with an uncertainty of ±11 cm^?1 at the worst or ±1 cm^?1 at best, depending upon the assignment of several very weak absorptions. The axial well depth, depending more critically upon these assignments, is no greater than 150 cm^?1 and may be as low as 5 cm^?1.     

Microwave spectrum of torsionally excited acetic acid

The microwave spectrum corresponding to the first excited state of the methyl torsion in acetic acid has been identified by means of microwave-microwave double resonance. Although the A-E splittings are extremely large, a reasonable fit has been obtained for the v = 0 and v = 1 states simultaneously by using a Hamiltonian which allows for geometry relaxation upon internal rotation. Barrier parameters are V₃ = 169.90 ± 0.06 cm^?1 and V₆ = ?6.74 ± 0.02 cm^?1. An interpretation of the parameters describing nonrigidity is given in terms of a model with two relaxing bond angles, which is qualitatively supported by ab initio calculations.     

Infrared,Raman, and microwave spectra of ethaneselenol and the determination of the barriers to internal rotation

The infrared, Raman, and microwave spectra of gaseous ethaneselenol have been investigated. The rotational constants for both the more stable gauche and for the trans conformers are reported for the Et⁷⁸SeH, Et⁷⁸SeD, Et⁸⁰SeH, and Et⁸⁰SeD isotopic species. A proposed structure has been derived from a least-squares analysis of the moments of inertia. Dipole moment components have been obtained from each conformer using second-order Stark effects. For the gauche conformer, they are μ_a = 1.42 ± 0.01, μ_c = 0.37 ± 0.03, and μ_total = 1.47 ± 0.01 D. For the trans isomer they are μ_a = 1.217 ± 0.002, μ_b = 0.850 ± 0.001, and μ_total = 1.485 ± 0.002 D. The methyl barrier to internal rotation was calculated using observed frequencies obtained from the infrared and Raman spectra; a value of 3.59 ± 0.01 kcal/mole was obtained. Asymmetric potential functions have been calculated for both the EtSeH and EtSeD isotopic species. For the light species the potential constants for internal rotation around the CSe bond are V₂ = ?96.4 ± 1, V₃ = 432 ± 4, and V₆ = ?20 ± 2 cm^?1. The difference between ground-state energy levels of the two conformers was found to be 66 cm^?1. A vibrational assignment based on infrared and Raman spectra of the gaseous phase is presented.     

Microwave spectrum and rotational isomerism of 3,3-difluoropropene CHF2CHCH2

The analysis of the microwave spectrum of 3,3-difluoropropene has confirmed the existence of two rotational isomers, cis and gauche. The rotational constants in the ground vibrational state are A = 9126.08 MHz, B = 3722.120 MHz, and C = 2946.598 MHz for the cis form and A = 8901.64 MHz, B = 4192.759 MHz, and C = 3107.718 MHz for the gauche form. The dipole moment and its components along the principal axes of intertia are μ_a = 2.369 ± 0.015 D, μ_c = 0.70 ± 0.03 D, and μ_t = 2.47 ± 0.03 D for the cis form and μ_a = 1.535 ± 0.015 D, μ_b = 0.53 ± 0.04 D, μ_c = 1.36 ± 0.03 D, and μ_t = 2.12 ± 0.05 D for the gauche form. The relative intensity measurement indicates that the cis form is more stable than the gauche form by 260 ± 80 cm^?1. The energy of the first excited state with respect to the ground state was found to be 63 ± 8 cm^?1 for the cis form and 85 ± 10 cm^?1 for the gauche form. Two Fourier coefficients of the potential function restricting the torsion around the CC bond were determined to be V₁ = 266 ± 40 cm^?1 and V₃ = 508 ± 200 cm^?1, using the available data. The potential function thus obtained is compared to a prediction model which is derived assuming additivity of the potential as a function of substitution.     

Analysis of torsional splittings in the microwave spectra of dimethylether,CH3OCH3 and its isotopes,CD3OCH3 and CD3OCD3

The multiplet splitting patterns of microwave transitions in the ground state and the first two torsional excited states of CH₃OCH₃, CD₃OCD₃, and CD₃OCH₃ were analyzed in terms of the semirigid rotor models C_2vF-C_3vT-C_3vT and $\text{C}{}_3\text{F-}\text{C}{}_{\mathrm{3v}}\text{T-}\text{C}{}_{\mathrm{3v}}\text{T}\text{?}$. The following nonzero potential coefficients were obtained for CH₃OCH₃: V₃₀ = V₀₃ = 909.05 ± 0.49 cm^?1, V′₃₃ = 5.06 ± 1.60 cm^?1; for CD₃OCH₃: V₃₀(CD₃) = 897.18 ± 2.41 cm^?1, V₀₃(CH₃) = 910.45 ± 0.33 cm^?1; for CD₃OCD₃: V₃₀ = V₀₃ = 897.00 cm^?1. These results are compared to earlier microwave studies of these molecules.     

Coherent Stokes and anti-Stokes Raman spectra of the ν1 (A1) and ν2 (E) bands of SF6 and UF6

Coherent Stokes and anti-Stokes Raman scattering are used to study the ν₁ and ν₂ spectral band profiles of UF₆ and SF₆. Most of the observed SF₆ “hot” bands are assigned, leading to evaluations of the anharmonicity constants X_ij: X₁₂ = ?(2.80 ± 0.30) cm^?1, X₁₄ = ?(1.00 ± 0.15) cm^?1, X₁₅ = ?(1.00 ± 0.15) cm^?1. For UF₆, a tentative assignment of the “hot” bands is made: X₁₂ = ?(1.80 ± 0.30) cm^?1, X₁₃ = ?(1.60 ± 0.30) cm^?1, X₁₄ = ?(0.20 ± 0.10) cm^?1, X₁₅ = ?(0.25 ± 0.10) cm^?1, and X₁₆ = ?(0.10 ± 0.05) cm^?1. Parameters such as the vibration-rotation coupling constants are determined. For SF₆: α = (7 ± 2) × 10^?5 cm^?1 for the ν₂ band and α = ?(1.02 ± 0.01) 10^?4 cm^?1 for the ν₁ band. The calculated spectral profiles of the coherent Stokes or anti-Stokes spectra, which are in good agreement with experimental results, give values for the resonant and nonresonant parts of the susceptibility in both molecules. They also show, in some cases, the influence of neighboring combination bands.     

Mößbauereffekt in FeCl2, FeSO4 und FeSO4 · 7 H2O

Mößbauereffect measurements were performed with FeCl₂, FeSO₄ and FeSO₄ · 7 H₂O in the temperature range between 5 and 300 ?K. The quadrupole splittings at 5 ?K were determined to be (1.300±0.027) mm/sec, (3.650±0.053) mm/sec, and (3.350±0.053) mm/sec respectively. From the temperature dependence of the quadrupole splittings it follows that in FeCl₂ the energy of the excited 3d-electron-level isδ=150 cm^?1, in FeSO₄ δ ₁=360 cm^?1 andδ ₂=1680 cm^?1 and in FeSO₄ · 7 H₂Oδ ₁=480 cm^?1 andδ ₂=1300 cm^?1. The magnitudes of the magnetic field at the iron nucleus at 5 ?K are (202±8) kOe for FeSO₄ and (0±4) kOe for FeCl₂.     

Vibrational spectra and force constants of symmetric tops: High-resolution spectra of H374Ge35Cl in the ν1ν4 region near 2100 cm−1

The gas-phase infrared spectrum of monoisotopic H₃⁷⁴Ge³⁵Cl has been studied in the ν₁, ν₄ region near 2100 cm^?1 with a resolution of 0.008 cm^?1. Rotational fine structure for ΔJ = ±1 branches has been resolved for both fundamentals. ν₁ (a₁), 2119.977 03(19) cm^?1; and ν₄ (e), 2128.484 65(8) cm^?1 are weakly coupled by Coriolis x,y resonance, Bξ_1,4^y 2.6 × 10^?3 cm^?1, and l-type resonance within ν₄, q₄⁽⁺⁾ ?8.4 × 10^?6 cm^?1, has been observed. An extended Fermi resonance with ν₅^±1 + 2ν₆^±2, which mainly affects the kl = ?14 and ?15 levels of ν₄, has been detected and analyzed. In addition, several weak and local resonances perturb essentially every K subband of ν₄ and some of ν₁, and a qualitative model is proposed to account for the features observed in the spectrum. Disregarding the transitions involved in local perturbations, the rms deviation of the fit to the remaining 2021 lines is σ = 1.34 × 10^?3 cm^?1.     

Infrared diode-laser spectrum of the CH3CN ν2 band: Analysis of local resonances with ν6±1 + 2ν8±2, ν4 + ν7±1 + ν8±1, ν4 + ν6±1, ν4 + ν7±1, and 2ν70 + ν8±1 states

Fifty-one sections of infrared diode-laser spectra of acetonitrile have been measured in the region from 2283.5 to 2235.7 cm^?1. About 450 transitions belonging to the ν₂ band have been assigned for K ≦ 7 and J ≦ 44. Anomalies found in the rotational structure have been proven to be due to five local resonances. Observed transition frequencies have been fitted by a least-squares method to a model which includes Fermi-type resonances (Δk = 0, Δ? = ± 3n) with ν₆^±1 + 2ν₈^±2 and ν₄ + ν₇^±1 + ν₈^±1 states, x, y-type Coriolis resonances (Δk = ±1, Δ? = ?3n ± 1) with ν₄ + ν₆^±1 and ν₄ + ν₇^±1 + ν₈^±1 states, and a centrifugal-distortion-type resonance (Δk = ±2, Δ? = ?3n ± 2) with a 2ν₇⁰ + ν₈^±1 state. The 11 × 11 dimensional energy matrix has been diagonalized in order to obtain the perturbed energy levels. The standard deviation for the fit is 1.075 × 10^?3 cm^?1. The molecular constants determined are also listed.     

Microwave spectra and barriers to internal rotation of trifluoroacetic acid and trifluoroacetyl fluoride

The rotational transitions of trifluoroacetic acid and trifluoroacetyl fluoride were identified with radiofrequency-microwave and microwave-microwave double resonance spectroscopy. Isotopic substitution of the hydrogen atom in trifluoroacetic acid showed that the hydrogen atom is cis with respect to the CO bond. A second conformation was not found. From A,E splittings in higher vibrational levels the internal rotation barriers were calculated: for trifluoroacetic acid, V₃ = 241.8 ± 0.5 cm^?1 (v = 4); for trifluoroacetyl fluoride V₃ = 383.6 ± 0.5 cm^?1 (v = 5).     

Gas phase infrared investigation of NOF3

Investigation of the partially resolved infrared bands of NOF₃ in the region 350–1800 cm^?1 leads to the following results: (i) the rotational constant B₀ is 0.19095 ± 0.00005 cm^?1, (ii) the Coriolis constants are ζ₄ = 0.94 ± 0.02, ζ₅ = ?0.015 ± 0.005, ζ₆ = ?0.38 ± 0.02, in fair agreement with the sum rule ζ₄ + ζ₅ + ζ₆ = 0.545 ± 0.045, (iii) Integrated intensities in km·mole^?1 for the most intense modes are: A₁ = 462, A₂ = 87.8, A₄ = 563. These three are estimated to be within 5% error.     

Pulsed dephotolysis in emulsion nanocrystals of silver halides: I. Recombination processes at early stages of photolysis

Early stages of formation of few-atom clusters of photolytic silver in AgBr nanocrystals are studied using the pulsed dephotolysis technique. It is shown that dephotolysis is characterized by a clearly pronounced dependence on the pulse duration of nonactinic and actinic radiations, the highest efficiency of dephotolysis being achieved for nanosecond pulses. The rate constant of recombination of free electrons with captured holes is determined (κ_p = (6 ± 1) × 10^?9 cm³ s^?1) and the dependence of the recombination rate on the level of excitation is found. The maximum recombination rate for the highest excitation level is found to be V _p ^max = 10⁹ s^?1 and the surface concentration of recombination centers is determined to be N _r = (2 ± 0.5) × 10¹¹ cm^?2.     

The microwave spectrum of a second N-gauche rotamer of allylamine

The microwave spectra of the ground and five excited states of a second gauche rotamer of allylamine have been measured and assigned. Three of the excited states belong to the same mode, most probably the CC torsion, the second and third vibrational states present a symmetrical splitting due to tunneling effect. The spectrum was conclusively identified as due to the N-gauche, lone-electron-pair trans form by means of the N-quadrupole coupling constants and dipole moment components. The variation observed for the quadrupole coupling constants in the different vibrationally excited states was explained by a suitable model. The ground state constants are (in MHz) A₀ = 23 957.05 ± 0.048, B₀ = 4 229.96 ± 0.025, C₀ = 4 154.91 ± 0.025, χ_aa = ? 1.48 ± 0.04, χ_bb - χ_cc = ? 1.42 ± 0.04, and (in D) ∥μ_a∥ = 0.766 ± 0.010, ∥μ_b∥ = 0.700 ± 0.005, ∥μ_c∥ = 0.290 ± 0.020.The excited states of the N-cis, lone-electron-pair trans form were also measured and assigned; two of these states appear to belong to the CC torsion as indicated by their intertial defects. The potential hindering the internal CC rotation was calculated using the relative intensity data of the N-cis and N-gauche forms as well as the tunneling splittings. A three-term cosine potential was fitted to the data yielding (in cm^?1) V₁ = ? 77 ± 85, V₂ = 170 ± 126, V₃ = 663 ± 95. The Dennison-Uhlenbeck potential was used for an approximate calculation of the N-trans barrier separating the two identical N-gauche forms. The barrier obtained was 1.9 ± 0.3 Kcal/mole.     

Infrared rotation-vibration spectra of ethane: The perpendicular band, ν7, of C2H6

The study of the gas-phase infrared spectrum of C₂H₆ in the region of the perpendicular CH-stretching band, ν₇, near 3000 cm^?1 is extended for the ΔK = + 1 subbands as far as K = 20. The spectral resolution of ～0.030 cm^?1 is increased to ～0.015 cm^?1 by deconvolution. The earlier investigation of this band for KΔK = +9 to ?5, is repeated with greater accuracy, providing more reliable ground-state constants (cm^?1): B₀ = 0.663089 ± 24, D₀^J = (0.108 ± 4) × 10^?5, D₀^JK = (0.50 ± 7) × 10^?5. The molecular constants (cm^?1) for the ν₇ fundamental are B₇ = 0.66310 ± 3, A₇ = 2.682, ν₀ = 2985.39, ζ₇ = 0.128. A discussion of resonance effects in this band, in particular x-y-Coriolis and Fermi resonance, is given.     

Laser photoluminescence spectra of the M+S2− species in solid argon at 12K

Matrix reactions of alkali metal atoms with S₂Cl₂ and photolyzed H₂S samples have been examined by laser excitation at 457.9 nm. The strong photoluminescence spectrum from 12 300 to 18 300 cm^?1 exhibited vibrational spacings near 550 cm^?1. Observation of the same ZPL spectrum with two different precursors identified the carrier as Na⁺S₂^?. The vibrational numbering was made possible by the Na⁺³²S³⁴S^? species in natural abundance and from a 33% ³⁴S-enriched sample of S₂Cl₂. The spectroscopic constants ν₀₀ = 19 990 ± 10 cm^?, ω₀″ = 586 ± 2 cm^?1 and ω₀x₀″ = 2.8 ± 0.2 cm^?1 are in excellent agreement with those reported for S₂^? in alkali halide crystals at low temperature.     

Line strengths,spin-splittings,and forbidden transitions in the (101) band of 14N16O2

Measurements of line strengths in the (101) and (111)-(010) bands of ¹⁴N¹⁶O₂ have been made at a resolution of 0.02 cm^?1 in the region 2863 to 2934 cm^?1. The strength data in the (101) band were analyzed to determine a vibrational band strength and coefficients of the F factor. Each subband for K_?1 ≤ 9 was analyzed separately and all the F-factor coefficients in terms of the rotational quantum number, N, were found to be too small to be of significance. However, F was found to be dependent on K_?1 and the experimentally determined subband strengths were least-squares fitted to the expression S_v⁰·F, where S_v⁰ = 68.3 cm^?2 atm^?1 at 296 K and F = 1 + (2.899 × 10^?3)K_?1 + (4.08 × 10^?3)K_?1² ? (2.34 × 10^?4)K_?1³. The integrated strengths for the (101) and (111)-(010) bands were found to be 70.9 ± 2.3 and 2.7 ± 0.3 cm^?2 atm^?1 at 296 K, respectively. Also included in this study are measurements of line center positions in the two bands and spin-splittings in the (101) band. Recent frequency measurements of lines with K_?1 ≤ 8 in the (101) band have been made at a resolution of 0.0033 cm^?1 by V. Dana and J. P. Maillard (J. Mol. Spectrosc.71, 1–4) (1978)) for the region above 2889 cm^?1 and our values are in excellent agreement with theirs. Separations of the split lines measured in this work (K_?1 ≤ 10) agree well with calculated values using expressions which include the η_aaaaK_?1⁴ term with η′_aaaa = ?1.70 ± 0.15 × 10^?4 cm^?1 as derived for the (101) state. Three forbidden (ΔN ≠ ΔJ, ΔK_?1 = 0) transitions in the (101) band were observed with their identifications based on the agreement between measured and calculated line positions and strengths.     

Mößbauereffekt in Eisenstilben und FeCl2·H2O

Using Mößbauer effect measurements in the temperature range between 3 °K and 310 °K the magnetic fields at the nucleus in iron-stilbene, FeCl₂·H₂O and FeCl₃ are determined to beH _T=0=(250±10) kOe, (252±18) kOe and (468±10) kOe; a Néel-temperature ofT _N=(23±1) °K is measured for iron-stilbene. The electric quadrupole splittings atT=0 °K for iron-stilbene and FeCl₂ ·H ₂ O, ΔE=(+2.52±0.02) mm/sec and (+2.50±0.05) mm/sec, yield electric field gradients at the iron nucleus ofq _z=+9.7·10¹⁷ V/cm² and +9.6·10¹⁷ V/cm², whereq _z⊥H; Debyetemperatures of θ=162 °K and 188 °K are obtained. The energy of the excited 3d-electron levels in iron-stilbene is estimated to Δ₁=309 cm^?1 and Δ₂=618cm^?1 as deduced from the temperature dependence ofΔE. In contrast to the suggestion ofEuler andWillstaedt bivalence of the iron in ironstilbene is found; its composition is shown to be 4(FeCl₂ ·H ₂O)·stilbene.     

Absolute intensity measurements of the CO2 bands 401III←000 and 411III←010

The absolute intensities of the transitions 401_III←000 and 411_III←010 of CO₂ have been measured from spectra obtained under high resolution. Both the vibration-rotation line intensities and the integrated band intensities are reported. The rotationless transition moment of 401_III←000 is deduced and a vibration-rotation interaction factor F(m) = 1+(4.92×10^?4)m+(4.4×10^?7)m² is determined. The values obtained are: S_Band(401_III←000) = (25.54±0.22)×10^?5 cm^?2atm_{(293 K)}^?1, |R₀₀₀^401_III| = (1.87±0.02)×10^?4D, and S_Band(411_III←010) = (1.83±0.13)×10^?5 cm^?2atm_{(293 K)}^?1.     

The ν4 and ν2 Raman bands of CHD3

The CHD₃ Raman spectrum from 1925 to 2455 cm^?1 has been photographed with a resolution of about 0.2 cm^?1, showing the overlapping ν₂ and ν₄ bands. Ground state combination differences yield C₀ = 2.6297 ± 0.0003 cm^?1. The ν₄ state is weakly perturbed, but reasonably accurate values could be obtained for ν₄ = 2250.88 ± 0.10 cm^?1, (Cζ)₄ = 0.656 ± 0.010 cm^?1, C₄ - C₀ and B₄ - B₀. Some of these constants differ significantly from values previously estimated by infrared workers. For the ν₂ state the constants determined are in good agreement with recent infrared results.