The vibrational and rotational spectra of ozone for the (0, 1, 0) and (0, 2, 0) states (original) (raw)
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Analysis of the 2ν1+ ν2+ 2ν3Band of Ozone
Journal of Molecular Spectroscopy, 1997
The 2n 1 / n 2 / 2n 3 band of ozone, occurring in the 4780 cm 01 region, has been observed for the first time, using a Fourier transform spectrometer, at 0.008 cm 01 resolution and using a large path length pressure product. Assignments of vibration-rotational transitions have been made up to J Å 48 and K a Å 9. As a few levels with K a Å 1 or 2 are perturbed, it has been necessary to take into account the Coriolis resonance between the and vibrational states. With the effective Hamiltonian explicitly accounting for the interaction between these two states, the fit on 165 energy levels leads to the rms deviation of 1.9 1 10 03 cm 01 , which is near the experimental accuracy. Line intensities of the 2n 1 / n 2 / 2n 3 band have been measured and calculated. The set of spectroscopic parameters for interacting bands, as well as transition moment constants, is given. A complete list of line positions and intensities, with a cutoff of 1 1 10 026 cm 01 /moleculercm 02 at 296 K up to J Å 65 and K a Å 15, has been generated, which leads to the integrated band intensity S v (2n 1 / n 2 / 2n 3 ) Å (5.1 { 2.0) 1 10 023 cm 01 /moleculercm 02 . ᭧ 1997 Academic Press 333
Journal of Quantitative Spectroscopy and Radiative Transfer, 2013
The state of the art analyses of high-resolution ozone spectra and a critical discussion of line parameters updated since the previous review by Rinsland et al. [J Quant Spectrosc Radiat Transfer 2003;82:207-18] are presented. We focus on recent works revisiting improved measurements and analyses of Fourier transform spectra below 5600 cm −1 and review Cavity Ring-Down Spectroscopy measurements and analyses in the 5850-7920 cm −1 spectral region which have been performed for 16 O 3 and all 18 O enriched ozone isotopologues. Various issues related to resonance perturbations due to dark states are discussed as well as the issues concerning the accuracy of the experimental parameters, the data modelling and the data reduction. Comparisons of vibration levels determined from spectra analyses with predictions from the molecular potential functions are given. The procedures of empirical corrections for calculated line lists are described and the "intricate" question of absolute intensity determination is overviewed. Also, a review of deficiencies, challenge for improvements, and related works in progress are reported.
Journal of Molecular Spectroscopy, 1998
Hot bands nu1 + 3nu2 - nu2 and 3nu2 + nu3 - nu2 of 16O3 in the region 2300-2600 cm-1 and the cold band 3nu2 + nu3 in the region 3050-3110 cm-1, corresponding to the v2 = 3 dyad {(130), (031)}, have been observed for the first time, using the Fourier Transform Spectrometer (FTS) at Reims and the usual experimental setup providing a large product pressure x path length, p x l. Three hundred sixty-five rovibration energy levels of the upper states were obtained with J and Ka up to 46 and 9, respectively. The fit of these data gives a r.m.s. deviation of 1.93 x 10(-3) cm-1. The v2 dependence of the rotational parameters A, B, and C for the (1v20) and (0v21) states is discussed. Copyright 1998 Academic Press. Copyright 1998Academic Press
International Journal of Quantum Chemistry, 1991
Potential energy surfaces, properties, and spectra of singlet (X ' A ,) and triplet (a3B2) ozone are investigated by means of MCSCF/MCLR analytical response theory calculations. MCSCF analytical gradients and Hessians are used to locate equilibrium and transition-state structures and to obtain associated vibrational and rotational constants, infrared intensities, and dipole moments. By means of MC linear response functions, electronic excitation energies, and oscillator strengths, static and dynamic polarizabilities as well as dispersion (C,) coefficients are obtained. Good agreement is achieved, in some cases within experimental error margins, for properties where experimental data are known. A very low IR intensity for triplet ozone is predicted.
The Journal of Physical Chemistry A, 2012
By use of the 3 1 A′ ab initio potential energy surface (PES) of ozone and the multi-configuration time-dependent Hartree program for wavepacket propagation, we have determined numerous eigenstates of this state for six ozone isotopologues. These bound vibrational levels are the upper levels of the Huggins band, which covers the range from 27 000 to ∼33 000 cm −1 . This study extends our previous work on the Hartley band, which was limited to the range ∼32 000−50 000 cm −1 . Four isotopologues, O 3 , 16 O 17 O 16 O, 16 O 18 O 16 O, and 18 O 3 (noted hereafter 666, 676, 686, and 888), are symmetric, and two are asymmetric, 17 O 16 O 2 and 18 O 16 O 2 (noted hereafter 667 and 668). The PES of the 3 1 A′ state has two equivalent minima of C s symmetry located at ∼27 000 cm −1 above the X 1 A 1 ground state. The equilibrium geometry of these two minima is r e 1 = 2.28 a 0 , r e 2 = 3.2 a 0 , and θ e = 107°. The dissociation limit of this PES, which correlates to the O( 1 D) + O 2 ( 1 Δ) "singlet" channel, is about 4300 cm −1 above the two minima. For the 16 O 3 isotopologue, the 120 lowest bound eigenstates have been calculated and partially assigned up to 800 cm −1 below the dissociation limit. The 60 lower eigenstates are easily assignable in term of three normal modes, the "long" bond (ν 1 ), the bending (ν 2 ), and the "short" bond (ν 3 ). A new family of wave functions, aligned along the dissociation channels, appears at 3782 cm −1 above the 3 1 A′ (0,0,0) level. The 3 1 A′ vibrational levels and the corresponding intensity factors from the (000), (010), (100), and (001) levels of the X 1 A 1 ground state have been calculated for the six isotopologues. The Huggins absorption cross sections of the six isotopologues have been calculated from the 3 1 A′ vibrational energy levels and the corresponding intensity factors. The rotational envelope of each vibronic band has been empirically described by an ad hoc function. The ratio of the Huggins cross section of each ozone isotopologue with one of 16 O 3 provides the fractionation factor of each ozone isotopologue as a function of the photon energy. These various fractionation factors will allow predicting enrichments due to photolysis by various light sources like the actinic flux.
Infrared spectra of 18O-enriched ozones in liquid oxygen solution
Chemical Physics, 1996
FTIR spectra of six ozone isotopomers are studied in liquid 0 2 solution at 77 K in the spectral range 650-3200 cm-1. Full vibrational assignment is given and relative transition strengths are measured for many previously unobserved 18 absorption bands of O-enriched species. Whenever such comparison is possible, most but not all of the relative strengths in solution are found to be in agreement with the rotationless transition moments in the gas phase. An order of magnitude enhancement observed for the hybrid-type v 1 transitions in asymmetric 160160180 and 160180180 molecules is consistent with the calculated off-diagonal vibrational dipole matrix elements for the fundamental transitions in C2v and C s isotopomers. It is suggested that enhancement of transitions into the states with the even vibrational quantum number u 3 may serve as a sensitive criterion for an interaction-induced asymmetric distortion of the 0 3 potential energy surface by intermolecular interactions via terminal oxygen atoms.
Journal of Molecular Spectroscopy
The very weak bands nu1 + 2nu2 + 3nu3 and 4nu1 + nu3 of 16O3 have been observed for the first time, using the Fourier transform spectrometer (FTS) of Reims and the usual experimental setup providing a large product p x l of approximately 38 Torr x 36 m. The upper levels of these A-type bands which are rather close in energy (they appear respectively at 5291.722 and 5307.790 cm-1) belong to two different sets of interacting polyads. To correctly reproduce the rotation-vibration energy levels and account for the observed perturbations, both bands are treated in a dyad approximation: the (123) state in the Coriolis resonance with the (330) state, and the (401) state in the Coriolis resonance with the (024) state. The assignments of the rotation-vibration levels of the (123) state are confirmed by measurements of line positions of the hot band nu1 + 2nu2 + 3nu3 - nu2 which has also been observed for the first time. The fits are very satisfactory: the r.m.s. deviation for 249 energy levels of the (123) state is 2.4 x 10(-3) cm-1 and is 2.0 x 10(-3) cm-1 for 266 levels of the (401) state. These r.m.s. are near experimental accuracy. Transition moments for the three observed bands are determined from measured line intensities. Copyright 1997 Academic Press. Copyright 1997Academic Press