Rotational coherence spectroscopy of para-difluorobenzene–Ar

Riehn, Christoph; Weichert, Andreas; Zimmermann, M.; Brutschy, Bernhard

doi:10.1016/s0009-2614(98)01236-6

Cited by 19 publications

(22 citation statements)

References 17 publications

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“…The rotational constant A 0 = 1135.3(6) MHz of the p-DFB· Ar van der Waals complex [13][14][15] is slightly smaller than the C 0 = 1138.9(5) MHz of p-DF B determined here. Since the equilibrium geometry of the Ar atom in p-DFB· Ar [13][14][15]44 is on the c inertial axis of p-DFB, these rotational constants should be equal for rigid p-DFB· Ar.…”

Section: B Determination Of Rotational Constantscontrasting

confidence: 71%

“…Since the equilibrium geometry of the Ar atom in p-DFB· Ar [13][14][15]44 is on the c inertial axis of p-DFB, these rotational constants should be equal for rigid p-DFB· Ar. The small difference probably arises from the contribution of the vibrational zeropoint motion of the Ar atom perpendicular to the p-DFB c axis.…”

Section: B Determination Of Rotational Constantsmentioning

confidence: 99%

“…The small difference probably arises from the contribution of the vibrational zeropoint motion of the Ar atom perpendicular to the p-DFB c axis. Based on the rotational constants of p-DFB· Ar, [13][14][15] we simulated its Raman RCS transient; no peaks were found that could be assigned to p-DFB· Ar.…”

Section: B Determination Of Rotational Constantsmentioning

confidence: 99%

“…15 They determined ground-and excited-state rotational constants for the p-DFB· Ar van der Waals complex from time-resolved fluorescence depletion using a near-symmetric oblate-top model. [13][14][15] Since the Ar atom lies on the c-axis of p-DFB, the reported A constant (1135.3(6) MHz) can be compared to the C rotational constant of p-DFB in this work, see Figure S1 16 of the supplementary material. In this work, we study the gas-phase rotational motion of p-DFB using time-resolved femtosecond Raman RCS, detected by degenerate four-wave mixing (DFWM) both in a supersonic jet and in a room-temperature gas cell.…”

Section: Introductionmentioning

confidence: 99%

“…12 More recently, Riehn et al investigated p-DFB and the p-DFB· Ar van der Waals complex using RCS spectroscopic methods. [13][14][15] For p-DFB, these workers were not able to fully simulate the transient at that time and did not determine any rotational constants. 15 They determined ground-and excited-state rotational constants for the p-DFB· Ar van der Waals complex from time-resolved fluorescence depletion using a near-symmetric oblate-top model.…”

Section: Introductionmentioning

confidence: 99%

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Rotational constants and structure of para-difluorobenzene determined by femtosecond Raman coherence spectroscopy: A new transient type

Den

Frey

Felker

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inAccurate rotational constant and bond lengths of hexafluorobenzene by femtosecond rotational Raman coherence spectroscopy and ab initio calculations J. Chem. Phys. 141, 194303 (2014) Femtosecond Raman rotational coherence spectroscopy (RCS) detected by degenerate four-wave mixing is a background-free method that allows to determine accurate gas-phase rotational constants of non-polar molecules. Raman RCS has so far mostly been applied to the regular coherence patterns of symmetric-top molecules, while its application to nonpolar asymmetric tops has been hampered by the large number of RCS transient types, the resulting variability of the RCS patterns, and the 10 3 -10 4 times larger computational effort to simulate and fit rotational Raman RCS transients. We present the rotational Raman RCS spectra of the nonpolar asymmetric top 1,4-difluorobenzene (para-difluorobenzene, p-DFB) measured in a pulsed Ar supersonic jet and in a gas cell over delay times up to ∼2.5 ns. p-DFB exhibits rotational Raman transitions with ∆J = 0, 1, 2 and ∆K = 0, 2, leading to the observation of J−, K−, A−, and C-type transients, as well as a novel transient (S-type) that has not been characterized so far. The jet and gas cell RCS measurements were fully analyzed and yield the ground-state (v = 0) rotational constants A 0 = 5637.68(20) MHz, B 0 = 1428.23(37) MHz, and C 0 = 1138.90(48) MHz (1σ uncertainties). Combining the A 0 , B 0 , and C 0 constants with coupled-cluster with single-, double-and perturbatively corrected triple-excitation calculations using large basis sets allows to determine the semi-experimental equilibrium bond lengths r e (C 1 -C 2 ) = 1.3849(4) Å, r e (C 2 -C 3 ) = 1.3917(4) Å, r e (C-F) = 1.3422(3) Å, and r e (C 2 -H 2 ) = 1.0791(5) Å. C 2015 AIP Publishing LLC. [http://dx

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