Analysis of the “Unusual” Vibrational Components of Triply Degenerate Vibrational Mode ν6 of Mo(CO)6 Based on the Classical Interpretation of the Effective Rotation–Vibration Hamiltonian

Dhont, Guillaume; Sadovskiı́, D.A.; Zhilinskii, B.I.; Boudon, Vincent

doi:10.1006/jmsp.2000.8070

Cited by 25 publications

(29 citation statements)

References 32 publications

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“…The high density of vibrational states, the presence of several hot bands, and the numerous possible anharmonic interactions prevented us from resolving the rotational structure in this part of the spectrum. Table III lists In the following paragraphs we present the first rotational analysis and fit of 7 fundamental bands of adamantane: ν 23 , ν 24 , ν 25 , ν 26 , ν 27 , ν 28 , and ν 30 . For the spectral analysis, it is possible to use the tools that have been developed previously for smaller tetrahedral molecules, importantly CH 4 .…”

Section: Resultsmentioning

confidence: 99%

“…The three spectra have been recorded with a spectral resolution of 0.001 cm −1 . All bands except ν 23 and ν 30 have been recorded using a globar continuum source together with an MCT detector and a KBr beamsplitter. In the first spectrum (600-4500 cm −1 ) the gas pressure was set to about 0.05 mbar (in order to optimize the detection of the ν 28 mode) and the acquisition time was about 24 h. In the second spectrum (33-600 cm −1 ) we have made use of the SOLEIL synchrotron FIR radiation extracted by the AILES beamline as the continuum source of the FT interferometer, resulting in a significant improvement of the signal-to-noise ratio in comparison with the globar source.…”

Section: A Experimentsmentioning

confidence: 99%

“…Polypropylene films of 50 μm thickness were used as cell windows. We injected the maximum vapor pressure attainable at room temperature (about 0.1 mbar) to detect and rotationally resolve the weak ν 30 band. Finally in the third spectrum (1000-2000 cm −1 ), the intense ν 28 mode has been recorded with a pressure of 0.01 mbar using the synchrotron source, KBr beamsplitter and MCT detector.…”

Section: A Experimentsmentioning

confidence: 99%

“…Previously, the biggest system that was investigated with the tensorial model developed in the Dijon group was molybdenum hexacarbonyl, Mo(CO) 6 , for which a single fundamental band has been modelled. 29,30 Adamantane thus offers a unique opportunity to apply these models to multiple vibrational bands, possibly with some interactions between some of them.…”

Section: Introductionmentioning

confidence: 99%

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Rotationally resolved infrared spectroscopy of adamantane

Pirali

Boudon

Oomens

et al. 2012

The Journal of Chemical Physics

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Rotationally resolved infrared spectroscopy of adamantanePirali, O.; Boudon, V.; Oomens, J.; Vervloet, M. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We present the first rotationally resolved spectra of adamantane (C 10 H 16 ) applying gas-phase Fourier transform infrared (IR) absorption spectroscopy. High-resolution IR spectra are recorded in the 33-4500 cm −1 range using as source of IR radiation both synchrotron radiation (at the AILES beamline of the SOLEIL synchrotron) as well as a classical globar. Adamantane is a spherical top molecule with tetrahedral symmetry (T d point group) and has no permanent dipole moment in its vibronic ground state. Of the 72 fundamental vibrational modes in adamantane, only 11 are IR active. Here we present rotationally resolved spectra for seven of them: ν 30 , ν 28 , ν 27 , ν 26 , ν 25 , ν 24 , and ν 23 . The typical rotational structure of spherical tops is observed and analyzed using the STDS software developed in the Dijon group, which provides the first accurate energy levels and rotational constants for seven fundamental modes. Rotational levels with quantum numbers as high as J = 107 have been identified and included in the fit leading to a typical standard deviation of about 10 −3 cm −1 .

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Section: Resultsmentioning

confidence: 99%

Section: A Experimentsmentioning

confidence: 99%

Section: A Experimentsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Rotationally resolved infrared spectroscopy of adamantane

Pirali

Boudon

Oomens

et al. 2012

The Journal of Chemical Physics

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“…In the case of the Hamiltonian (11.4) whose vibrational part is quadratic, this approximation matches exactly the extrema of the so-called "rotational energy surfaces" [32,36,35], which are obtained when all rotational operators in H eff are replaced by their quantum analogues. Further examples can be found in [58,13,12].…”

Section: Examplesmentioning

confidence: 99%

Analysis of Rotation--Vibration Relative Equilibria on the Example of a Tetrahedral Four Atom Molecule

Efstathiou¹,

Sadovskií²,

Zhilinskii³

2004

SIAM J. Appl. Dyn. Syst.

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Abstract. We study relative equilibria (RE) of a nonrigid molecule, which vibrates about a well-defined equilibrium configuration and rotates as a whole. Our analysis unifies the theory of rotational and vibrational RE. We rely on the detailed study of the symmetry group action on the initial and reduced phase space of our system and consider the consequences of this action for the dynamics of the system. We develop our approach on the concrete example of a four-atomic molecule A4 with tetrahedral equilibrium configuration, a dynamical system with six vibrational degrees of freedom. 1. Introduction. This paper unifies modern methods of classical theory of symmetric Hamiltonian dynamical systems and quantum theory of molecules (and other isolated finiteparticle systems). Considerable progress was achieved in both directions in the last decades and deep relations between these seemingly distant theories became evident. Significant effort by mathematicians and molecular physicists to converge the two fields resulted in the qualitative theory of highly excited quantum molecular systems based on recent mathematical developments. We join the two approaches and demonstrate what kind of concrete results can be immediately obtained in molecular systems [1,2,3,4] by applying powerful methods of symmetric Hamiltonian systems [5,6,7,8,9,10,11]. We choose a concrete problem of rotation-vibration of a four-atomic molecule with tetrahedral equilibrium configuration [12,13] in order to explain the details of our approach.

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Spherical Top Theory and Molecular Spectra

Boudon

Champion

Gabard

et al. 2011

Handbook of High‐resolution Spectroscopy

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In this article, we present an overview of the present state of the art of the theory of high‐resolution spherical‐top spectra in the framework of the effective Hamiltonian approach. We describe the specific features of this class of molecules to explain the basic concepts of the theoretical methods used for the analysis (line positions and intensities) and the simulation of absorption (including pure rotation) and Raman spectra of such species. The non conventional formalism that we use is essentially based on irreducible tensor methods and is especially adapted to computational treatments and global analyses of complex interacting band systems. We give examples concerning mainly methane (CH 4 ) and sulfur hexafluoride (SF 6 ). The efficiency of these methods is not restricted to spherical tops, as they also apply to other molecular species or spectroscopic problems. We demonstrate this through recent developments including the modeling of the effects of collisions on line shapes, the modeling of rovibronic effects, as well as extensions to molecules with lower symmetry. The computer implementation of the methods is an integral part of the modeling. We conclude the article with an overview of the free access programs and databases developed in the Dijon group for spherical‐top molecules and some other species.

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Analysis of the “Unusual” Vibrational Components of Triply Degenerate Vibrational Mode ν6 of Mo(CO)6 Based on the Classical Interpretation of the Effective Rotation–Vibration Hamiltonian

Cited by 25 publications

References 32 publications

Rotationally resolved infrared spectroscopy of adamantane

Rotationally resolved infrared spectroscopy of adamantane

Analysis of Rotation--Vibration Relative Equilibria on the Example of a Tetrahedral Four Atom Molecule

Spherical Top Theory and Molecular Spectra

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