Line assignments and global analysis of the tunneling-rotational microwave absorption spectrum of dimethyl methylphosphonate

Line assignments were carried out for about 600 Fourier-transform microwave transitions for dimethyl methylphosphonate involving levels of all six symmetry species in the G₁₈ molecular symmetry group appropriate for three large-amplitude motions and covering J and K values of 1?J?6 and 0?|K|?3. The assignments are based on combination-difference loops, variations in line shape for different symmetry species caused by the small internal-rotor splitting patterns of the third, high-barrier methyl top, and agreement with theoretically expected positions. A global fit of 609 lines to a phenomenological tunneling-rotational Hamiltonian with 54 constants was performed, yielding a standard deviation of 8.0 kHz, which is close to the experimental measurement uncertainty. The A/E tunneling splitting for the lowest barrier methyl group internal rotation motion was determined indirectly to be about 34 GHz. The much smaller tunneling splitting for the methoxy interchange motion was determined (with some assumptions) to be 3.3 MHz.     

Methyl torsional state analysis of the jet-cooled microwave spectrum of N-acetylglycine

The microwave spectrum of N-acetylglycine was obtained using a NIST Fourier-transform microwave spectrometer equipped with a heated, pulsed-nozzle source. One conformer has been identified and its spectrum assigned. The conformer has C_S point group symmetry and an intramolecular hydrogen bond between the carbonyl and amide groups of the 5-membered glycine unit. Internal rotation of the methyl rotor group leads to splitting of the rotational lines into A and E symmetry tunneling states. The ¹⁴N nuclear-quadrupole hyperfine structure verifies the rotational and internal-rotor state assignments. The V₃ barrier of 57.5(1) cm⁻¹ and the angles between the C₃ axis of the methyl rotor and the principal inertial axes are in best agreement with the calculated values for the lowest energy conformer of the four conformers predicted at the MP2/6-311++G(d,p) level of theory.     

Analysis of the pure-rotational spectrum in the ν28 = 1 excited torsional state and torsional couplings of trans-ethyl methyl ether

The trans-ethyl methyl ether molecule has three low-lying torsional modes, that is, two inequivalent methyl internal rotations and an asymmetric skeletal torsion. The internal rotations of the CCH₃ and OCH₃ methyl rotors and the skeletal torsion correspond to the vibrational modes, ν₂₈, ν₂₉ and ν₃₀ respectively. In this study, the microwave absorption spectrum in the ν₂₈ = 1 CCH₃ torsional state was analyzed for the first time. Nine hundred fifty seven lines up to J = 48 and K = 4 were assigned, and the rotational, centrifugal distortion and internal rotational tunneling parameters were determined with the use of a tunneling matrix formalism. By combining the present results on the ν₂₈ = 1 torsional state with those for the ν₃₀ = 1 skeletal torsional state and the ν₂₉ = 1 OCH₃ torsional state, torsional couplings are estimated in order to understand quantitatively the inverted A/E sequence patterns observed for those three excited torsional states.     

Coherence-converted population transfer FTMW-IR double resonance spectroscopy of CH3OD in the OD-stretch region

Rotationally selected infrared spectra of jet-cooled CH₃OD have been recorded and analyzed in the OD-stretch region (2710-2736 cm⁻¹). The observed spectra are obtained by monitoring three E-species microwave transitions (1₋₁ ← 1₀ at 18.957 GHz, 2₋₁ ← 2₀ at 18.991 GHz, and 3₋₁ ← 3₀ at 19.005 GHz) in a narrowband cavity Fourier transform microwave spectrometer, using the background-free coherence-converted population transfer technique. Of the four upper state subbands observed, two (K′ = 0 and −2) are split by perturbations. The E-species deperturbed band origin is at 2718.1 cm⁻¹. The deperturbed reduced term values follow a pattern similar to the ground state. This allows the J′ = 0 torsional tunneling splitting to be estimated as 2.1 cm⁻¹, which can be compared to 2.6 cm⁻¹ in the ground state.     

The rotational spectrum of the ground state of methylamine

Recent progress is reported in measuring, assigning, and fitting the rotational spectrum of the ground vibrational state of methylamine, CH₃NH₂, a spectrum complicated both by internal rotation of the methyl top and by inversion of the amino group. New measurements of 513 rotational transitions with J up to 30 and K up to 9 were carried out between 49 and 326 GHz using the millimeter-wave spectrometer in Kharkov. After removing the observed quadrupole hyperfine splittings, these new data along with previously published measurements were fitted to a group-theoretical high-barrier tunneling Hamiltonian from the literature, using 53 parameters to give an overall weighted standard deviation of 0.80 for 850 far-infrared and 673 microwave transitions in the ground state. The root-mean-square deviation of 0.018 MHz obtained for 346 millimeter-wave transitions measured with 0.020 MHz uncertainty represents an approximately 30-fold improvement in fitting accuracy over past attempts.     

Electrical characterization of deep levels in n-type GaAs after hydrogen plasma treatment

Deep level transient spectroscopy (DLTS) and Laplace-DLTS (L-DLTS) have been used to investigate defects in an n-type GaAs before and after exposure to a dc hydrogen plasma (hydrogenation). DLTS revealed the presence of three prominent electron traps in the material in the temperature range 20-300 K. However, L-DLTS with its higher resolution enabled the splitting of two narrowly spaced emission rates. Consequently four electron traps at, E_C—0.33 eV, E_C—0.36 eV, E_C—0.38 eV and E_C—0.56 eV were observed in the control sample. Following hydrogenation, all these traps were passivated with a new complex (presumably the M3), emerging at E_C—0.58 eV. Isochronal annealing of the passivated material between 50 and 300 °C, revealed the emergence of a secondary defect, not previously observed, at E_C—0.37 eV. Finally, the effect of hydrogen passivation is completely reversed upon annealing at 300 °C, as all the defects originally observed in the reference sample were recovered.     

Analysis of the rotational spectrum of pyruvonitrile up to 324 GHz

The room-temperature rotational spectrum of pyruvonitrile (acetyl cyanide, CH₃COCN) was measured up to 324 GHz, and additional measurements were also made in supersonic expansion in the region 7-19 GHz. The available data sets for the A and E torsional sublevels were extended to over 1200 transitions, J = 65 and K_a = 38 for the ground vibrational state, and to comparable numbers of transitions for first excited states of the methyl torsional mode ν₁₈, and the in-plane CCN bending mode ν₁₂. The collected experimental measurements were fitted with several different computer programs for dealing with the effects of methyl torsional motion on the rotational spectrum and many spectroscopic constants have been determined. The experimental results are discussed in detail and are augmented by ab initio computations. Stark effect measurements in supersonic expansion were used to precisely determine the electric dipole moment of pyruvonitrile, ∣μ_a∣ = 2.462(2) D, ∣μ_b∣ = 2.442(2) D, μ_tot = 3.468(2) D. Pyruvonitrile, as an 8-atom molecule with a sizable dipole moment, is a possible candidate for astrophysical detection and the present work provides the laboratory data necessary for that purpose.     

Influence of atomic hydrogen annealing on the optical properties of vacuum-deposited a-Si:H films

The influence of atomic hydrogen annealing on the optical parameters of a-Si:H films was studied using spectrophotometric measurements of the film transmittance and reflectance in the wavelength range 200-3000 nm. In this annealing, the deposition of a thin layer and treatment with atomic hydrogen were repeated alternately, where the thickness of the thin cyclic layer, d_cyc, and the treatment time of each cycle, t_ca, were kept fixed for each sample. A series of different samples with average thickness of 0.5 μm and different d_cyc and t_ca were prepared. It was found that the refractive index, n, and the optical energy gap, E_g, increase as the treatment time, t_ca, increases from 0 to 60 s, while at t_ca=120 s both n and E_g decrease. Also, both the refractive index and the optical energy gap decrease with increasing the relative diffusion length of hydrogen, √t_ca/d_cyc from 0.39 to 0.77. The widening of E_g is due to the structural relaxation resulting from impingement of atomic hydrogen on the growing surface. Thus, a good-quality a-Si:H with Urbach parameter 65 mev and optical energy gap of 1.78 eV was successfully prepared.     

Microwave structural studies of organoselenium compounds 1. Microwave spectra, molecular structure, and methyl barrier to internal rotation of dimethyl diselenide

The rotational spectra of nine isotopomers of dimethyl diselenide, CH₃SeSeCH₃, have been measured with a molecular-beam Fourier transform microwave spectrometer. The spectra were complex due to the presence of many isotopomers in natural abundance and the splitting caused by the interactions with two methyl internal rotors. The spectra were assigned and fit to experimental precision to an effective rotational Hamiltonian for molecules with two periodic internal motions. The spectra of the symmetric isotopomers are consistent with a C₂ equilibrium structure. The rotational constants were used to determine the r_s structure of the C-Se-Se-C frame with the results r(SeSe)=2.306(3) Å, r(SeC)=1.954(6) Å, ?(CSeSe)=99.8(2)°, ?(CSeSeC)=85.2(1)°. A barrier to internal rotation of the methyl groups of 395 ± 2 cm⁻¹ was derived from the internal rotation splittings.