The near infrared spectrum of ozone by CW-cavity ring down spectroscopy between 5850 and 7000 cm(-1): new observations and exhaustive review

Weak vibrational bands of (16)O(3) could be detected in the 5850-7030 cm(-1) spectral region by CW-cavity ring down spectroscopy using a set of fibered DFB diode lasers. As a result of the high sensitivity (noise equivalent absorption alpha(min) approximately 3 x 10(-10) cm(-1)), bands reaching a total of 16 upper vibrational states have been previously reported in selected spectral regions. In the present report, the analysis of the whole investigated region is completed by new recordings in three spectral regions which have allowed: (i) a refined analysis of the nu(1) + 3nu(2) + 3nu(3) band from new spectra in the 5850-5900 cm(-1) region; (ii) an important extension of the assignments of the 2nu(1)+5nu(3) and 4nu(1) + 2nu(2) + nu(3) bands in the 6500-6600 cm(-1) region, previously recorded by frequency modulation diode laser spectroscopy. The rovibrational assignments of the weak 4nu(1) + 2nu(2) + nu(3) band were fully confirmed by the new observation of the 4nu(1) + 2nu(2) + nu(3)- nu(2) hot band near 5866.9 cm(-1) reaching the same upper state; (iii) the observation and modelling of three A-type bands at 6895.51, 6981.87 and 6990.07 cm(-1) corresponding to the highest excited vibrational bands of ozone detected so far at high resolution. The upper vibrational states were assigned by comparison of their energy values with calculated values obtained from the ground state potential energy surface of (16)O(3). The vibrational mixing and consequently the ambiguities in the vibrational labelling are discussed. For each band or set of interacting bands, the spectroscopic parameters were determined from a fit of the corresponding line positions in the frame of the effective Hamiltonian (EH) model. A set of selected absolute line intensities was measured and used to derive the parameters of the effective transition moment operator. The exhaustive review of the previous observations gathered with the present results is presented and discussed. It leads to a total number of 3863 energy levels belonging to 21 vibrational states and corresponding to 7315 transitions. In the considered spectral region corresponding to up to 82% of the dissociation energy, the increasing importance of the "dark" states is illustrated by the occurrence of frequent rovibrational perturbations and the observation of many weak lines still unassigned.     

Transformation of the effective rotational Hamiltonian of nonrigid X 2 Y molecules

The transformation of the effective rotational Hamiltonian H of nonrigid X ₂ Y molecules to the form having a minimum number of diagonals in the basis of rotational functions of a symmetric top is discussed. Such a transformation is a generalization of the reduction transformation performed for the polynomial effective Hamiltonian H. It is shown that in the general case the transformation substantially changes the form of the initial Hamiltonian, which restricts the region of applicability (J<J*) of the reduced Hamiltonian represented in a class of elementary functions in terms of angular momentum operators. The values of the rotational quantum number J* are estimated for the (000) ground and (010) vibrational states of the H₂O molecule.     

Extension of the MIRS computer package for the modeling of molecular spectra: From effective to full ab initio ro-vibrational Hamiltonians in irreducible tensor form

The MIRS software for the modeling of ro-vibrational spectra of polyatomic molecules was considerably extended and improved. The original version [Nikitin AV, Champion JP, Tyuterev VlG. The MIRS computer package for modeling the rovibrational spectra of polyatomic molecules. J Quant Spectrosc Radiat Transf 2003;82:239–49.] was especially designed for separate or simultaneous treatments of complex band systems of polyatomic molecules. It was set up in the frame of effective polyad models by using algorithms based on advanced group theory algebra to take full account of symmetry properties. It has been successfully used for predictions and data fitting (positions and intensities) of numerous spectra of symmetric and spherical top molecules within the vibration extrapolation scheme. The new version offers more advanced possibilities for spectra calculations and modeling by getting rid of several previous limitations particularly for the size of polyads and the number of tensors involved. It allows dealing with overlapping polyads and includes more efficient and faster algorithms for the calculation of coefficients related to molecular symmetry properties (6C, 9C and 12C symbols for C_3v, T_d, and O_h point groups) and for better convergence of least-square-fit iterations as well. The new version is not limited to polyad effective models. It also allows direct predictions using full ab initio ro-vibrational normal mode Hamiltonians converted into the irreducible tensor form. Illustrative examples on CH₃D, CH₄, CH₃Cl, CH₃F and PH₃ are reported reflecting the present status of data available. It is written in C++ for standard PC computer operating under Windows. The full package including on-line documentation and recent data are freely available at http://www.iao.ru/mirs/mirs.htm or http://xeon.univ-reims.fr/Mirs/ or http://icb.u-bourgogne.fr/OMR/SMA/SHTDS/MIRS.html and as supplementary data from the online version of the article.     

Complete nuclear motion Hamiltonian in the irreducible normal mode tensor operator formalism for the methane molecule

A rovibrational model based on the normal-mode complete nuclear Hamiltonian is applied to methane using our recent potential energy surface [A. V. Nikitin, M. Rey, and Vl. G. Tyuterev, Chem. Phys. Lett. 501, 179 (2011)]. The kinetic energy operator and the potential energy function are expanded in power series to which a new truncation-reduction technique is applied. The vibration-rotation Hamiltonian is transformed systematically to a full symmetrized form using irreducible tensor operators. Each term of the Hamiltonian expansion can be thus cast in the tensor form whatever the order of the development. This allows to take full advantage of the symmetry properties for doubly and triply degenerate vibrations and vibration-rotation states. We apply this model to variational computations of energy levels for (12)CH(4), (13)CH(4), and (12)CD(4).     

Vibrational spectra of ternary ordered vacancy compounds

We have studied the lattice dynamics of A²B ₂ ³ C ₄ ⁵ crystals with the thiogallate structure using a nonpolarized ion model. We computed the interatomic interaction parameters for nine compounds. The calculated phonon spectra, density of vibrational states, and temperature dependence of the specific heats agree well with the available experimental data. V. D. Kuznetsov Siberian Physicotechnical Institute, Tomsk University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 85–89, February, 1998.     

Accurate relations for the isotopically invariant spectroscopic parameters of diatomic molecules

Equations are obtained relating the isotopically invariant spectroscopic parameters U_mj, which must be considered as conditions in the least-squares method in spectral analysis. Expressions are given for the first seven Dankhem potential parameters in terms of U_m0 and U_m1. The contribution to the spectroscopic coefficients Y_mj due to violation of the Born-Oppenheimer approximation is calculated for¹²C¹⁶O.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 18–21, November, 1984.It remains to thank Yu. S. Makushkin, V. Ya. Galin, andV. F. Golovko for valuable discussions of the work.     

V2-dependence of centrifugal constants of H2O molecules in the Morse oscillator model

It is shown in this paper that the centrifugal constantsC ^l (t) calculated in the Morse, oscillator model for the sequence from the operator H _red ^(t) , which is used in processing the rotational levels of the H₂O molecule, are linked by recurrence relations, which enables H _z ^(t) –H _z ^(O) to be given in closed form.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 56–58, October, 1982.     

Shape resonances in slow electron scattering by aromatic molecules. I. Anthraquinone derivatives

A series of anthraquinone (C(14)O(2)H(8)) derivatives has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), photoelectron spectroscopy (PES), and AM1 quantum chemical calculations. Mean lifetimes of molecular negative ions M(-.) (MNI) have been measured. The mechanism of long-lived MNI formation in the epithermal energy region of incident electrons has been investigated. A simple model of a molecule (a spherical potential well with the repulsive centrifugal term) has been applied for the analysis of the energy dependence of cross sections at the first stage of the electron capture process. It has been shown that a temporary resonance of MNI at the energy approximately 0.5 eV corresponds to a shape resonance with lifetime 1-2.10(-13) s in the f-partial wave (l = 3) of the incident electron. The next resonant state of MNI at the energy approximately 1.7 eV has been associated with the electron excited Feshbach resonance (whose parent state is a triplet npi* transition). In all cases the initial electron state of the MNI relaxes into the ground state by means of a radiationless transition, and the final state of the MNI is a nuclear excited resonance with a lifetime measurable on the mass spectrometry timescale. Copyright 1999 John Wiley & Sons, Ltd.     

Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MS(n)) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C(14)-C(19) fatty acids, some of which were monounsaturated. Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type. The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations. The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MS(n) spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS(2) spectra of [M + K](+) ions, it was established that all components have a C(15:0) fatty acid at the sn-2 position of the glycerol backbone and C(14)-C(19) acids at the sn-1 position of the glycerol backbone. Copyright 1999 John Wiley & Sons, Ltd.     

The 2003 edition of the GEISA/IASI spectroscopic database

The content of the current (2003) version, GEISA/IASI-03, of the computer-accessible spectroscopic database, GEISA/IASI, is described. This “system” or database is comprised of three independent spectroscopic archives, which are (a) a database of individual spectral line parameters on 14 molecules, H₂O, CO₂, O₃, N₂O, CO, CH₄, O₂, NO, SO₂, NO₂, HNO₃, OCS, C₂H₂, N₂, and the related 51 isotopomers and isotopologues, representing 702,550 entries, in the spectral range 599-, (b) a database of spectral absorption cross-sections (6,572,329 entries related to six molecules, CFC-11, CFC-12, CFC-14, HCFC-22, N₂O₅, CCl₄), and a catalogue of microphysical and optical properties (mainly, the refractive indices) of atmospheric aerosols. The modifications and improvements, which have been implemented since the earlier editions of this database, in terms of content and management, have been explained in detail. GEISA/IASI has been created with the specific purpose of assessing the capability of measurement by the IASI instrument within the designated goals of ISSWG in the frame of the CNES/EUMETSAT European Polar System preparation.All the archived data can be handled through a user-friendly associated management software, which is posted on the ARA/LMD group web site at http://ara.lmd.polytechnique.fr.