The global processing of a set of observed positions of spectral lines in the A2Σ+→X2П, B2Σ+→A2Σ+, and A2Σ+→A2Σ+ electronic transitions, collected from available literature has been performed. The analysis is based on a global model, which assumes the vibrational dependence of the parameters of the effective Hamiltonian for a given electronic state. As a result of processing a more extensive data set, new parameters of the "Dunham" type were obtained for the A2Σ+ electronic state, which make it possible to simulate the vibrational-rotational energy levels for the OH radical in the A2Σ+ electronic state.
The global processing of a set of experimental frequencies of electronic-vibrational-rotational transitions collected from available literature has been performed. As a result of global processing, involving the vibrational dependence of the parameters, "Dunham type" coefficients were found for A2Σ and molecular constants for the B2Σ, C2Σ electronic states of the 16OH radical.
The results of critical evaluation of measured rotation-vibration line positions of 16OH in the X2 Π state are presented. The analysis was carried out using the fundamental Rydberg-Ritz combination principle, for the available experimental data in the spectral range 101-10358 cm-1. As a result, the precise set of 990 experimental energy levels of OH molecule in the interval 0-35665 сm-1 was obtained. Comparisons with the HITRAN and with known calculated energy levels are discussed.
The global fitting of the experimental energy levels of unresolved Λ-doublets for the ground state of 14N16O molecule is done. The dataset of 1789 experimental energy levels covering the 0-35665 cm-1 interval for 23 vibrational states was obtained using the fundamental Rydberg-Ritz combination principle. A global model of analysis with vibrational dependences of the parameters of the effective Hamiltonian was used for the theoretical treatment of the diatomic molecule in 2Π electronic state. As a result of the fit a set of the "Dunham-type" molecular parameters was obtained. They reproduce the dataset of the experimental energy levels to the precision of the experimental ones. The found set of the parameters was compared with previous set determined by C.Amiot.
The results of critical evaluation of measured rotation-vibration line positions of 14N16O in the X2π state are presented. The analysis was carried out using the fundamental Rydberg-Ritz combination principle, for the available experimental data in the spectral range 1700-7400 cm-1 which represent unresolved Λ-doublets. As a result, the precise set of 1802 experimental energy levels of NO molecule in the interval 0-35665 сm-1 were obtained. Comparisons with the HITRAN and with the calculated energy levels from C.Amiot (1982) are discussed.
The results of the LMR spectra calculation in the 0-1 band of the NO molecule are presented. For the simulation of the spectra in a strong magnetic field the special numerical model was developed. This model allows one to calculate the dependence of Zeeman splitting of ro-vibrational lines of the NO molecule on the intensity of a strong magnetic field. The analysis of temporal behavior of the absorption coefficients of CO laser radiation on thirteen lines in the variable magnetic field was done.
The results of experimental and theoretical study of the Zeeman splitting of the vibrational-rotational lines in the NO molecule as a function of magnetic field are presented. To record the spectrum the method of laser magnetic resonance (LMR) with using continuous wave frequency-tunable CO laser has been applied. To analyze experimental data of Zeeman splitting, the calculation procedure was developed. This procedure is based on the numerical diagonalization the matrix of the effective molecular Hamiltonian, which includes Zeeman operator corresponding to interaction an external magnetic field with a molecule.
Thanks to the record ofnew FTS spectra of O3 in the 4300 cm1 region, the 122-000 band is now observed. Assignments
of line transitions for following values of rotational quantum numbers J and Ka: 10 < J < 51 , Ka ≤ 8 were done. In the
linelist about 443 transitions of v1+2v2+2v3 band are presented. To correctly reproduce the obtained energy levels of
(122) state, the very weak "dark state" (400) was introduced. A data reduction has been done using effective Hamiltonian
for three interacting states {400, 122 023}, which are coupled through the usual Coriolis and high order rotational and
vibrational resonances. The final fit on the 589 energy levels is quite satisfactory. The root mean square deviation
between observed and calculated values is about O.0029cm-1. The fit of line intensities allows us to derived transition
moment parameters for 2v2+3v3 and v1+2v2+2v3 bands.
The effective dipole moment operators for the interacting fundamental nondegenerate vn bands of different symmetry
and degenerate Vt bands are presented. Using symmetry properties of the effective dipole moment parameters, the
transition moments are expressed and well-known Herman-Wallis factors are constructed. The case of strong Z-resonances
between fundamentals is considered.
One of the features of the H2S molecule is quite weak intensity of the fundamental bands. Another feature is anomalous distribution of intensity over branches and its dependence on the rotational quantum number K. Correctly calculated parameters of the dipole moment function for the H2S molecule allowed us to estimate the first and second rotational corrections in the transition moment operator for the fundamental bands. The calculated corrections appeared from the vibration-rotation coupling well reproduce the unusual intensity pattern of the P, Q and R branches in the H2S molecule.
New analysis is performed of a body of data on v2 band line intensities of the water molecule involving mainly the transitions reported by R. A. Toth. As a theoretical approach the formalism of the effective-dipole moment operators is used. We have been able to determine eight effective-dipole moment parameters, which result in a satisfactory agreement between observed and calculated intensities. The total RMS deviation of the fit is 6%.
Using symmetry arguments effective vibrational-rotational Hamiltonians for bending vibrational levels of C2H2 and C2D2 have been written up to the fourth order in the Amat-Nielsen ordering scheme. These Hamiltonians describe all bending energy levels of molecules in ground electronic state. Hamiltonian for C2D2 contains Darling- Dennison resonance interaction terms (2(omega) 4 is congruent to 2(omega) 5). The latter differs slightly from that used by T.R. Huet, M. Herman, and J.W.C. Johns. It contains additional terms. It has been shown that these effective Hamiltonian are ambiguous. The transformations to the reduced form have been suggested.
In this paper we continue to investigate the effective Hamiltonians for the C4v and D2d molecules and consider the case of Z-resonances. There exist C4v and D2d molecules having strong Coriolis resonances between their fundamental bands. These Coriolis resonances can be classified according to the component of angular momentum in Coriolis interaction operator. It is usual practice to take the main symmetry axis as z-axis of molecular- fixed frame. In this case Z-resonances take place between degenerate or nondegenerate vibrational levels.
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