Rotational analysis of the NO2 6125-Å region

In the NO₂ 6125-Å region 135 transitions belonging to four bands have been assigned using laser-induced fluorescence. On the whole, the rotational structure of the four vibronic bands is well characterized by near-prolate symmetric top relations. The 6125 and 6126-Å bands perturb each other, the former having predominantly the character of the $\text{A}\text{?}{}^2\text{B}{}_2$ state, the latter the $\text{X}\text{?}{}^2\text{A}{}_1$ state; this parent-daughter relationship is recognized to occur else-where in the NO₂ visible spectrum.     

Rotational analysis of the 7390- and 7937-Å bands of NO2 by means of Fourier transform spectroscopy

We have extended to higher N and to K_a = 3 and 4 the rotational analysis of the 7390-Å band of NO₂ performed by K. E. Hallin and A. J. Merer (Canad. J. Phys.55, 2101–2112 (1977)). The lines belong to a perturbed parallel band for which Hallin and others have proposed the vibrational assignment (2 13 1)-(0 0 0) within the electronic ground state. These authors presumed that this band borrows its intensity through a vibronic coupling (spin-orbit and/or Coriolis coupling) from the stronger (0 2 0)-(0 0 0) band of the $\text{A}\text{?}\text{-}\text{X}\text{?}$ electronic system at 7460 Å. We have observed about 900 transitions belonging to the K_a = 0, 1, 2, 3, 4 subbands of the (2 13 1)-(0 0 0) band for N values going up to about 23, and 300 lines of the “hot” band (2 13 1)-(0 1 0). We have also looked for spin-orbit-induced transitions and we have detected about 400 transitions with ΔN ≠ ΔJ. Among them ΔN = ±2 transitions with ΔK_a = 0 or ± 2 have been observed, indicating that N and K_a are no longer good quantum numbers, and demonstrating clearly the existence of rovibronic interactions perturbing the upper levels of the transitions.     

Rotational analysis of bands in the high-resolution infrared spectra of the three species of butadiene-1,4-d2; refinement of the assignments of the vibrational fundamentals

Samples of trans,trans and cis,cis forms of butadiene-1,4-d₂ have been synthesized and found to contain useful amounts of the cis,trans species as a contaminant. Assignments of fundamental frequencies for the three isotopomers of butadiene-1,4-d₂ have been extended and improved from investigations of their Raman spectra as well as their infrared (IR) spectra. High-resolution IR spectra have been recorded for the three isotopomers, and a rotational analysis has been completed for strong bands of each species. Ground state and some upper state rotational constants have been fit. Corresponding ground state moments of inertia compare favorably with equilibrium moments of inertia obtained from B3LYP/6-311++G** theory. Two ¹³C isotopomers are being prepared, and an improved structural analysis of butadiene will soon be available to assess how π-electron delocalization affects its structure.     

Rotational line strengths in the Lyman and Werner bands of H2

Rotational line strengths in the Lyman and Werner bands of molecular hydrogen are affected by the nonadiabatic interaction between the B and C states. Numerical results are presented for the effect of this interaction on relative rotational line strengths for V_x = 0 and V_B ≤ 25, V_c ≤ 9. The B-C interaction is shown to have a pronounced effect for many levels. This difference in rotational line strength factors from the usual Hönl-London factors should be taken into account when relating line oscillator strengths to band oscillator strengths. Relative rotational line strengths are also computed for transitions between C-state levels and excited vibrational levels in the X state. Comparison is made to the measured Werner band emission line intensities of Schmoranzer and Geiger [J. Chem. Phys., 59, 6153 (1973)].     

Investigation of collision-induced absorption in the vibrational fundamental bands of O2 and N2 at elevated temperatures

Collision-induced absorption has been measured for the vibrational fundamental bands of N₂ and O₂ at temperatures up to 360 K. These data when combined with previously obtained lower temperature data show that the integrated band intensity of the O₂ fundamental increases as the temperature is raised above 300 K. The integrated intensity of the N₂ band also increases, but at a much lower rate with temperature.     

Uniaxial stress measurements on Rb2PbCu(NO2)6 and K2PbCu(NO2)6

EPR measurements on crystals of compressed tetragonal Rb₂PbCu(NO₂)₆ and K₂PbCu(NO₂)₆ subjected to uniaxial stress have been carried out at various temperatures. The results indicate that uniaxial stress can reorient the crystal axes in both compounds and that smaller stresses are required for Rb₂PbCu(NO₂)₆ than for K₂PbCu(NO₂)₆ at comparable temperatures. Larger stresses are required at lower temperatures.     

The vibrational transition moment for the ν2 bands of 14ND3 and 15ND3

Intensities were measured at high pressure (200 Torr) for blended K-multiplets in the P and R branches of the s0 → aν₂ and a0 → sν₂ bands of ¹⁴ND₃. Intensities of 55 individual lines at 10 Torr of ¹⁵ND₃ were also measured by deconvolution of the true line shape from the observed vibration-rotation spectrum and the instrumental line shape. From these results we estimate a transition moment of 0.179 ± 0.010 D for both ¹⁴ND₃ and ¹⁵ND₃. These lead to a derivative of the dipole moment, $\text{|}\text{?μ}\text{?Q}{}_2\text{| = 93}\text{cm}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{sec}{}^{\mathrm{?1}}$.     

Rotational analyses of the four fundamental bands,equilibrium structure,and general quadratic force field of PD3

The four fundamental bands of PD₃ were recorded with a Fourier transform infrared spectrometer at a resolution of 0.06 cm^?1. These bands were rotationally analyzed with explicit inclusion of the ν₁-ν₃ and ν₂-ν₄ Coriolis interactions. A rotational perturbation was found in the ν₄ band and was interpreted as due to a Δk = ±3-type interaction. New relations among the Coriolis constants of the XY₃ molecule with C_3v symmetry were derived and used for the analysis. Equilibrium structure, the L matrix elements, and general quadratic force field of the PD₃ molecule were determined.     

Rotational analysis of the ν1, 2ν1 and 5ν1 stretching bands of HGeD3

The high-resolution spectrum of the ν₁=5 stretching overtone of gaseous H⁷⁰GeD₃ has been recorded by an intracavity laser absorption spectrometer based on a vertical external cavity surface emitting laser (VECSEL). The rotational structure of the excited state at 9874.605 cm⁻¹ was found weakly perturbed by unidentified interaction with dark states. Finally, of the 313 lines rotationally assigned, 239 lines were found unperturbed and could be reproduced with a root-mean-square (rms) deviation of 0.012 cm⁻¹. The retrieved set of rotational parameters agrees with the values extrapolated from the previously studied ν₁=6-8 stretching overtones. High-resolution FTIR spectra of the ν₁ and 2ν₁ bands have also been recorded and analyzed. The ν₁=1 level, (ν_eff=2114.15 cm⁻¹) is in anharmonic interaction with a further A₁ symmetry level (ν_eff=2102.39 cm⁻¹). The potential coupling term could be estimated (W_anh=5.6(3) cm⁻¹) and the most probable assignment of the perturber is ν₂+ν₃. Moreover both levels are rotationally perturbed in an irregular fashion. Only a coarse analysis up to J=6 could be performed. The 2ν₁ band reveals irregular perturbations of medium intensity by unknown dark states for almost all K values. Nevertheless the obtained leading rovibrational parameters of the 2ν₁ band for J?6 are in agreement with those of the ν₁=5-8 states.     

Microwave-optical double resonance in NO2

A series of experiments performed to establish the nature of the previously reported microwave optical double resonance signals in electronically excited nitrogen dioxide are reported. The DC stark effect, hyperfine spectrum, and microwave saturation behavior of the double resonance signals observed by exciting NO₂ with the 4880 Å line of an argon ion laser have been studied. The data presented support the assignment of this double resonance signal as occurring within the rovibronic manifold of the ²B₂ electronic state. The observation of a number of new excited state microwave transitions is also reported.     

Triple quantum MQMAS spectroscopy of (I=7/2) in Na3Co(NO2)6 and trans-Co[(en2)(NO2)2]NO3 interplay between the quadrupole coupling and anisotropic shielding tensors

The purpose of this paper is to investigate the interplay between the chemical shielding anisotropy and quadrupole interaction in MQMAS spectra. in the compounds Na₃Co(NO₂)₆ and trans-Co[(en₂)(NO₂)₂]NO₃ provides model systems for such an investigation. Furthermore, only few results have been reported on the application of the MQMAS method to a spin I=7/2. The possibilities of the MQMAS spectroscopy for determining the relative orientation of the two tensors and its advantage over previous techniques are discussed. Reported experimental spectra at different spinning speeds of Na₃Co(NO₂)₆ are accurately reproduced by our theoretical simulations. The calculations are based on a recent approach, summarized in the present paper, which allows one to perform efficient simulations of MQMAS spectra including all interactions and their time-dependence throughout the experiment. This is necessary for calculating accurate MQMAS spectra including the spinning sideband pattern. In the case of trans-Co[(en₂)(NO₂)₂]NO₃ where the quadrupolar interaction and chemical shielding are stronger and their axes are non-coincident, the MQMAS spectrum is strongly distorted due to the unsufficient spinning speed and RF power. In this case, MAS at different spinning speeds is shown to provide valuable information.     

Opto-galvanic spectroscopy of some molecules in discharges: NH2, NO2, H2 and N2

The change of the discharge voltage when laser light crossing the discharge is tuned to a molecular transition has been measured. Experiments have been performed in the wavelength region between 570 nm and 620 nm with discharges in NH₃, NO₂, H₂, N₂, O₂ and argon. Transitions from the ground states of NH₂ and NO₂ and transitions from metastable states of N₂ and H₂ have been detected. The spacial dependence of the opto galvanic in a low pressure dc-discharge of H₂ and N₂ has been studied.     

Preparation of WO3 nanoparticles and application to NO2 sensor

WO₃ nanoparticles were prepared by evaporating tungsten filament under a low pressure of oxygen gas, namely, by a gas evaporation method. The crystal structure, morphology, and NO₂ gas sensing properties of WO₃ nanoparticles deposited under various oxygen pressures and annealed at different temperatures were investigated. The particles obtained were identified as monoclinic WO₃. The particle size increased with increasing oxygen pressure and with increasing annealing temperature. The sensitivity increased with decreasing particle size, irrespective of the oxygen pressure during deposition and annealing temperature. The highest sensitivity of 4700 to NO₂ at 1 ppm observed in this study was measured at a relatively low operating temperature of 50 °C; this sensitivity was observed for a sensor made of particles as small as 36 nm.     

Rotational energy cluster formation in XY3 molecules: Excited vibrational states of BiH3 and SbH3

Previous theoretical work on energy cluster formation at high rotational excitation in the vibrational ground state of PH₃ [S.N. Yurchenko, W. Thiel, S. Patchkovskii, P. Jensen, Phys. Chem. Chem. Phys. 7 (2005) 573] is extended to BiH₃ and SbH₃. By means of variational calculations of the rotation–vibration energies based on ab initio potential energy surfaces, we analyze the rotational energy clustering of BiH₃ and SbH₃ at J  70 for a number of vibrational states. We show that BiH₃ and SbH₃, with their pronounced local mode behaviour, exhibit cluster formation already at moderate rotational excitation. In addition, owing to its quasi-spherical-top character, BiH₃ undergoes an imperfect bifurcation at high J. This gives rise to an energy cluster type not present in PH₃ and SbH₃. We present a semi-classical approach to the construction of the rotational energy surfaces for vibrationally excited states.     

Core electron ionization energies and electronic structure of Ti(NO3)4 and Cu(NO3)2

Gas phase X-ray photoelectron spectra of Ti(NO₃)₄ and Cu(NO₃)₂ are reported and discussed in terms of the molecular charge distributions. No measurable splitting is observed between the 1s ionization energies of the chemically distinct oxygen atoms in either molecule. Ab initio calculations for Cu(NO₃)₂ suggest that this is due in large measure to differential orbital relaxation occurring upon core electron ionization.     

Brillouin spectroscopy in K2Ba(NO2)4

The temperature dependence of elastic stiffnesses of K₂Ba(NO₂)₄ is investigated in the range - 140 to + 160°C, in which two phase transitions have been reported. Marked anomalies appear at the lower transition, in contrast with continuous variations through the upper transition. Results are compared to those obtained near the upper transition by an ultrasonic method and they are qualitatively discussed.     

Submillimeter-wave spectroscopy of HN2 and DN2 in the excited vibrational states

The pure rotational transitions of HN₂⁺ and DN₂⁺ in the first excited vibrational states for all the fundamental vibrational modes have been observed in the range of 300-750 GHz. The molecular constants determined are much more accurate compared with those obtained from the infrared spectroscopy. The equilibrium rotational constants, B_e = 46832.45 (71) MHz for HN₂⁺ and B_e = 38708.38 (58) MHz for DN₂⁺, have been determined by correcting for the higher-order vibration-rotation interaction effects, γ_ij, obtained by an infrared investigation. The equilibrium bond lengths are derived from these equilibrium rotational constants: r_e(H-N) = 1.03460 (14) Å and r_e (N-N) = 1.092698 (26) Å.