Doppler-free two-photon spectroscopy of the 2ν3 band of SF6

Patterson, Chris W.; Herlemont, F.; Azizi, M.; Lemaire, J.

doi:10.1016/0022-2852(84)90284-4

Cited by 26 publications

(11 citation statements)

References 18 publications

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“…R cm is determined as 4.15772(2) Å where the ground‐state effective moments of inertia of the isolated monomers14, 15 are used for ${I_{bb}^{{\rm{NH}}_{\rm{3}} } }$ , ${I_{cc}^{{\rm{NH}}_{\rm{3}} } }$ and ${I_{bb}^{{\rm{SF}}_{\rm{6}} } }$ . Millen16 has provided an expression that allows the calculation of the quadratic stretching force constant for the weak bond between NH 3 and SF 6 moieties [Eq.…”

Section: Resultsmentioning

confidence: 99%

The σ‐Hole Interaction Between Sulfur Hexafluoride and Ammonia Characterised by Broadband Rotational Spectroscopy

et al. 2015

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A weakly-bound complex of SF6 and NH3 is generated within an expanding gas jet and characterised by broadband rotational spectroscopy. The spectra of isotopologues (32) SF6 ⋅⋅⋅(14) NH3 , (32) SF6 ⋅⋅⋅(14) ND3 , (32) SF6 ⋅⋅⋅(15) NH3 and (34) SF6 ⋅⋅⋅(15) NH3 are observed and assigned to determine the spectroscopic parameters. These parameters are consistent with the complex having a C3v symmetric rotor geometry, in which the nitrogen atom of NH3 coordinates to SF6 such that the C3v axis of the NH3 sub-unit is aligned with a local C3 axis on the SF6 sub-unit. The geometry of the complex is rationalized in terms of a σ-hole interaction. The observed spectra and ab initio calculations also reveal evidence of internal dynamics involving internal rotation of one monomer sub-unit with respect to the other about the symmetry axis of the complex.

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Section: Resultsmentioning

confidence: 99%

The σ‐Hole Interaction Between Sulfur Hexafluoride and Ammonia Characterised by Broadband Rotational Spectroscopy

et al. 2015

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“…A centrifugal stabilization energy, dE, is defined, as before [6-g], as the difference between the energy of an assumed rigid molecule (Q = Qo, the usual equilibrium structure) with angular momentum J and that of the non-rigid molecule with the same J AE= [E,(Q,) +&(Q,,J) I-[E,(Q) +EAQ,J) 1 (4) The resulting information maybe re-expressed, if desired, in terms of spectroscopic constants, as described previously [ 6-91.…”

Section: General Methodsmentioning

confidence: 99%

Molecules with high rotational angular momentum: a generalized ab initio approach

Lohr

1989

Journal of Molecular Structure: THEOCHEM

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An outline is given of a systematic and automated computational procedure based upon our successful ab initio approach to the theoretical study of centrifugal distortions of rotating molecules and their associated energy stabilizations. Such a generalized procedure permits the ready evaluation of the centrifugal distortion spectroscopic constants for moderate-sized molecules of low or no symmetry; these molecules represent cases for which the older version of our computational procedure is unwieldy. More broadly, we explore the energies and geometries of molecules in those regions of nuclear coordinate hyperspace which are accessible by such distortions from the equilibrium geometry. A method is outlined for optimizing the geometry of a molecule in the presence of a centrifugal field which is parametrically dependent upon the rotational angular momentum. The field is not fixed for a given angular momentum, but is coupled with the geometry via the moment of inertia tensor. This development should prove to be of major benefit to both computational chemists and molecular spectroscopists, as it will advance the interplay of theoretical and experimental studies of molecular structure.

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“…The 2ν 3 band is of g symmetry (with A 1g , E g , F 2g sublevels), and is therefore forbidden for infrared direct one-photon absorption. A study of this band using Doppler Free Two-Photon spectroscopy is reported in [7]. The 3ν 3 band is of u symmetry (with A 2u , F 2u , 2F 1u sublevels), and is infrared active.…”

Section: The ν 3 Bandmentioning

confidence: 99%

The high overtone and combination levels of SF 6 revisited at Doppler-limited resolution: A global effective rovibrational model for highly excited vibrational states

Faye

Boudon

Loëte

et al. 2017

Journal of Quantitative Spectroscopy and Radiative Transfer

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Sulfur hexafluoride is an important prototypal molecule for modeling highly excited vibrational energy flow and multi quanta absorption processes in hexafluoride molecules of technological importance. It is also a strong greenhouse gas of anthropogenic origin. This heavy species, however, features many hot bands at room temperature (at which only 30 % of the molecules lie in the ground vibrational state), especially those originating from the lowest, v 6 =1 vibrational state. Using a cryogenic long path cell with variable optical path length and temperatures regulated between 120 and 163K , coupled to Synchrotron Radiation and a high resolution interferometer, Doppler-limited spectra of the 2ν 1 + ν 3 , ν 1 + ν 2 + ν 3 , ν 1 + ν 3 , ν 2 + ν 3 , 3ν 3 , ν 2 + 3ν 3 and ν 1 + 3ν 3 from 2000 to 4000 cm-1 near-infrared region has been recorded. Low temperature was used to limit the presence of hot bands. The spectrum has been analyzed thanks to the XTDS software package. Combining with previously observed weak difference bands in the far infrared region involving the v 1 , v 2 , v 3 =1 states, we are thus able to use the tensorial model to build a global fit of spectroscopic parameters for v 1 =1,2, v 2 =1, v 3 =1,2,3. The model constitutes a consistent set of molecular parameters and enable spectral rovibrational simulation for all multi-quanta transitions involving v 1 , v 2 and v 3 up to v 1−3 =3. Tests simulation on rovibrational transitions not yet rovibrationally assigned are presented and compared to new experimental data.

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Doppler-free two-photon spectroscopy of the 2ν3 band of SF6

Cited by 26 publications

References 18 publications

The σ‐Hole Interaction Between Sulfur Hexafluoride and Ammonia Characterised by Broadband Rotational Spectroscopy

The σ‐Hole Interaction Between Sulfur Hexafluoride and Ammonia Characterised by Broadband Rotational Spectroscopy

Molecules with high rotational angular momentum: a generalized ab initio approach

The high overtone and combination levels of SF 6 revisited at Doppler-limited resolution: A global effective rovibrational model for highly excited vibrational states

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