High‐resolution Rotational<scp>R</scp>aman Coherence Spectroscopy with Femtosecond Pulses

Frey, Hans‐Martin; Kummli, Dominique S.; Lobsiger, Simon; Leutwyler, Samuel

doi:10.1002/9780470749593.hrs055

Cited by 23 publications

(17 citation statements)

References 63 publications

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“…2,20,21 Briefly, three parallel laser beams from an amplified Ti:Sapphire laser system provide the ∼75 fs pulses at 800 nm employed for the stimulated Raman pump, dump, and probe steps. The stimulated Raman polarization induced by the pump/dump steps at time zero is detected by the DFWM signal generated from the time-delayed probe pulse.…”

Section: Experimental Methodsmentioning

confidence: 99%

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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Section: Experimental Methodsmentioning

confidence: 99%

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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“…The work on (H 2 O) n clusters can be found in reviews of Saykally and coworkers (Liu et al 1994, 1997, Gregory et al 1997, Paul et al 1997, Keutsch et al 2003. Some of the work of the Leutwyler group is covered in this handbook by Frey et al (2011): High-resolution Rotational Raman Coherence Spectroscopy with Femtosecond Pulses, this handbook. The theoretical work related to experiment is far too exclusive to be covered here, but several articles in this handbook deal with the theoretical aspects.…”

Section: Organization Of the Articlementioning

confidence: 99%

High‐ResolutionFTIRand Diode Laser Spectroscopy of Supersonic Jets

Snels

Horká‐Zelenková

Hollenstein

et al. 2011

Handbook of High‐resolution Spectroscopy

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Fourier transform infrared (FTIR) spectrometers and tunable diode lasers in combination with a supersonic molecular beam expansion are a perfect tool for the investigation of molecules, ions, and radicals at low temperatures. The internal degrees of freedom of the molecules are adiabatically cooled to very low temperatures and thus only low-lying energy levels are populated. The reduction of the number of populated levels at low temperatures makes the assignment of the spectra much easier as compared to the congested room-temperature spectra. Under certain conditions, the Doppler linewidths are greatly reduced, corresponding to very low effective translational temperatures. Supersonic expansion also provides a suitable method for producing and investigating van der Waals clusters and hydrogen-bonded complexes. Unstable species such as radicals and ions can be efficiently produced and studied in a molecular beam. The low rotational temperature allows for the study of nuclear spin symmetry conservation or conversion between nuclear spin isomers. A molecular beam expansion can be obtained by expanding gas through a slit or a circular nozzle. Both expansion geometries can be used in combination with a multipass optical setup and with cavity ring down spectroscopy, which enhances the effective absorption path length. Cooling of the molecules can be promoted by seeding in noble gases. This article summarizes the general aspects of the experimental technique as well as current developments. To demonstrate how powerful the combination of a molecular beam expansion with tunable diode laser and FTIR spectroscopy can be, we report results on some important current examples.

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“…Our rotational constants agreed well with all literature values from high-resolution rovibrational spectroscopy (see Table 1). Kummli and coworkers (7,9) reported a significantly different rotational constant of B = 3.271 549 2 (±18) GHz for the main CS2 isotopologue ground state, based on RCS spectroscopy. (The striking 18 sigma deviation of this value from ours and literature values may be due to a typographic error: The tabulated rotational constant in ref.…”

Section: Discussion and Outlookmentioning

confidence: 99%

“…Felker (4) and coworkers developed a number of experimental schemes under the label rotational coherence spectroscopy (RCS). RCS was used to analyze the rotational structure of molecules and clusters with small or no dipoles (5)(6)(7)(8)(9). The highest resolution RCS experiments scanned opto-mechanical delays up to 2 m (10,11) and observed rotational wave packets over a time range ∆t ≤ 6 ns.…”

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Mass-correlated rotational Raman spectra with high resolution, broad bandwidth, and absolute frequency accuracy

Schröter

Lee

Schultz

2018

Proc. Natl. Acad. Sci. U.S.A.

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We present mass-correlated rotational alignment spectroscopy, based on the optical excitation of a coherent rotational quantum wave and the observation of temporal wave interferences in a mass spectrometer. Combined electronic and opto-mechanical delays increased the observation time and energy resolution by an order of magnitude compared with preceding time-domain measurements. Rotational transition frequencies were referenced to an external clock for accurate absolute frequency measurements. Rotational Raman spectra for six naturally occurring carbon disulfide isotopologues were resolved with 3 MHz resolution over a spectral range of 500 GHz. Rotational constants were determined with single-kilohertz accuracy, competitive with state-of-the-art frequency domain measurements.

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High‐resolution RotationalRaman Coherence Spectroscopy with Femtosecond Pulses

Cited by 23 publications

References 63 publications

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

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

High‐ResolutionFTIRand Diode Laser Spectroscopy of Supersonic Jets

Mass-correlated rotational Raman spectra with high resolution, broad bandwidth, and absolute frequency accuracy

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