High-resolution Raman spectroscopy of the ν1 region and Raman–Raman double resonance spectroscopy of the 2ν1−ν1 band of 32SF6 and 34SF6. Determination of the equilibrium bond length of sulfur hexafluoride

Boudon, Vincent; Doménech, José Luis; Bermejo, Dionisio; Willner, Helge

doi:10.1016/j.jms.2004.04.006

Cited by 25 publications

(15 citation statements)

References 30 publications

(53 reference statements)

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“…Indeed, complex vibrational dynamics of SF 6 were investigated by high-order harmonic spectroscopy in 2006 by Wagner et al [13], using an impulsive stimulated Raman excitation (ISR) in a colinear pump-probe setup. Among the six normal modes of SF 6 , three are Raman active: υ 1 -fully symmetric and strongly active mode A 1g with a quantum of 774 cm −1 (vibrational period of ≈ 43 fs), υ 2 the doubly degenerated mode E g with a quantum of 643 cm −1 (≈ 52 fs) and finally the triply degenerated υ 5 -T 2g mode with a quantum of 524 cm −1 (≈ 63 fs) [14]. ISR is quite inefficient in SF 6 with relatively long (25-30 fs) pump pulses, so that only the first vibrational excited state was populated in [13], resulting in very weak distorsions of the molecular bond geometry as a function of pump-probe delay.…”

Section: Introductionmentioning

confidence: 99%

High-order harmonic transient grating spectroscopy of SF₆molecular vibrations

Ferré¹,

Staedter²,

Burgy³

et al. 2014

J. Phys. B: At. Mol. Opt. Phys.

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Strong field transient grating spectroscopy has shown to be a very versatile tool in time-resolved molecular spectroscopy. Here we use this technique to investigate the high-order harmonic generation from SF6 molecules vibrationally excited by impulsive stimulated Raman scattering. Transient grating spectroscopy enables us to reveal clear modulations of the harmonic emission. This heterodyne detection shows that the harmonic emission generated between 14 to 26 eV is mainly sensitive to two among the three active Raman modes in SF6, i.e. the strongest and fully symmetric υ1-A1g mode (774 cm −1 , 43 fs) and the slowest mode υ5-T2g (524 cm −1 , 63 fs). A time-frequency analysis of the harmonic emission reveals additional dynamics: the strength and central frequency of the υ1 mode oscillate with a frequency of 52 cm −1 (640 fs). This could be a signature of the vibration of dimers in the generating medium. Harmonic 11 shows a remarkable behavior, oscillating in opposite phase, both on the fast (774 cm −1 ) and slow (52 cm −1 ) timescales, which indicates a strong modulation of the recombination matrix element as a function of the nuclear geometry. These results demonstrate that the high sensitivity of high-order harmonic generation to molecular vibrations, associated to the high sensitivity of transient grating spectroscopy, make their combination a unique tool to probe vibrational dynamics.

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Section: Introductionmentioning

confidence: 99%

High-order harmonic transient grating spectroscopy of SF₆molecular vibrations

Ferré¹,

Staedter²,

Burgy³

et al. 2014

J. Phys. B: At. Mol. Opt. Phys.

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“…Using the present results and those of the previous studies of 1 [15] and of the 3 [10] and 4 [12] infrared bands, we can now calculate the isotopic shifts for all the SF 6 fundamentals, i.e.…”

Section: Isotopic Shiftsmentioning

confidence: 58%

“…The precise absolute value of the 6 harmonic frequency is still unknown. Thus, as before [10][11][12]15], we considered that it should be approximately 346.9 cm À1 for 32 SF 6 . We also made the approximation that the A 1g sublevel of 2 6 lies exactly at 2 6 ' 693:8 cm À1 (again for 32 SF 6 ), i.e.…”

Section: The 2m 6 Overtone Bandmentioning

confidence: 99%

“…However, as we have shown in a recent review article [9] and in previous papers [10][11][12][13][14][15], the spectroscopy of this molecule, which is essential for quantitative measurements in the atmosphere, is still insufficiently known. In particular, the region of the 3 fundamental near 948 cm À1 is of primary importance since its very strong absorption is responsible for the huge greenhouse capabilities of SF 6 .…”

Section: Introductionmentioning

confidence: 99%

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High-resolution stimulated Raman spectroscopy and analysis of the ν ₂, ν ₅ and 2ν ₆ bands of ³⁴SF₆

et al. 2006

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The 2 , 5 and 2 6 regions of 34 SF 6 have been studied by stimulated Raman spectroscopy. We used an isotopically pure sample of 34 SF 6 . A detailed analysis of the 2 and 5 fundamentals has been performed with the HTDS program suite (http://www.u-bourgogne.fr/LPUB/ hTDS.html) dedicated to octahedral XY 6 molecules. We also present a preliminary analysis of the 2 6 band for both 32 SF 6 and 34 SF 6 . Finally, we give the 32 SÀ 34 S isotopic shifts for all the SF 6 fundamentals.

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“…We have used the experimental equilibrium geometry, in which SF 6 is an octahedron with central S nucleus, external F nucleus and R SÀF ¼ 1.5560 Å [21], which gives for equilibrium inertia momentum of the molecule the following value: I e ¼ 3.0552 Â 10 À38 g cm 2 . The nuclear g F value was taken to be 5.26 [6] .…”

Section: Computational Detailsmentioning

confidence: 99%

Nuclear spin–spin constants, rotationalgfactor and susceptibility of sulphur hexafluoride

Palma

Santos

2012

Molecular Physics

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Following our previous study on spin-rotation and shielding constants of the SF 6 molecule, the rotational g factor and the magnetic susceptibility are calculated here, using ab initio methods to evaluate the electronic contribution to the nuclear hyperfine constants, and compared with experimental results. It is shown, for the first time, that the electronic component of the rotational g factor is proportional to a constant, which is given by a sum over electronic states. We also evaluate for the SF 6 molecule the indirect, or electron-coupled spin-spin interaction, theoretically described by Ramsey, and show that it gives non-negligible corrections to direct coupling constants d 1 and d 2 . The contributions of the terms included in this interaction (DSO, PSO, SD and FC) are also analysed. IntroductionThe study of nuclear hyperfine interactions in molecules, namely the nuclear spin-spin constants and rotational g tensor, has lead to many important applications in physics, chemistry, biology and medicine. The development of the theoretical formalism and methods of calculation suitable for their interpretation requires a continued research effort.In the 1970s and 1980s hyperfine structures were recorded with ultra-high resolution in the vibration-rotation molecular spectra of highly symmetric molecules [1][2][3][4]. The hyperfine constants were expressed by the sum of nuclear constants and electronic constants expressed by second-order perturbation theory as a summation over a complete set of excited states inaccessible by hand calculation. More recently, in the last twenty years, the hyperfine interactions have been also studied within the framework of the NMR experiments.In a recent work [5], we studied the hyperfine structures detected in the spectra of highly symmetric molecules (particularly O h point group). We reported the spin-rotation and the shielding constants, which were obtained using tensorial formalism and ab initio methods to evaluate the electronic contribution.Using a similar approach and ab initio methods to evaluate the electronic contributions, we discuss in the present work how the rotational g factor, included in

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High-resolution Raman spectroscopy of the ν1 region and Raman–Raman double resonance spectroscopy of the 2ν1−ν1 band of 32SF6 and 34SF6. Determination of the equilibrium bond length of sulfur hexafluoride

Cited by 25 publications

References 30 publications

High-order harmonic transient grating spectroscopy of SF₆molecular vibrations

High-order harmonic transient grating spectroscopy of SF₆molecular vibrations

High-resolution stimulated Raman spectroscopy and analysis of the ν ₂, ν ₅ and 2ν ₆ bands of ³⁴SF₆

Nuclear spin–spin constants, rotationalgfactor and susceptibility of sulphur hexafluoride

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High-resolution Raman spectroscopy of the ν1 region and Raman–Raman double resonance spectroscopy of the 2ν1−ν1 band of 32SF6 and 34SF6. Determination of the equilibrium bond length of sulfur hexafluoride

Cited by 25 publications

References 30 publications

High-order harmonic transient grating spectroscopy of SF6molecular vibrations

High-order harmonic transient grating spectroscopy of SF6molecular vibrations

High-resolution stimulated Raman spectroscopy and analysis of the ν 2, ν 5 and 2ν 6 bands of 34SF6

Nuclear spin–spin constants, rotationalgfactor and susceptibility of sulphur hexafluoride

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Product

Resources

About

High-order harmonic transient grating spectroscopy of SF₆molecular vibrations

High-order harmonic transient grating spectroscopy of SF₆molecular vibrations

High-resolution stimulated Raman spectroscopy and analysis of the ν ₂, ν ₅ and 2ν ₆ bands of ³⁴SF₆