Rapid capture of large amplitude motions in 2,6-difluorophenol: High-resolution fast-passage FT-MW technique

Jahn, Michaela K.; Dewald, David A.; Wachsmuth, Dennis; Grabow, Jens‐Uwe; Mehrotra, S. C.

doi:10.1016/j.jms.2012.07.006

Cited by 35 publications

(24 citation statements)

References 21 publications

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“…Passage-Acquired-Coherence technique) spectrometer [42] between 7-16 GHz. Further measurements were made using the COBRA (Coaxially Aligned Beam ResonatorA rrangement) Fourier Tr ansform Microwaves pectrometer, [43] which prolongs the observation time comparedtoaFabry-Perottype cavity setup used in the style of Balle and Flygare [44] to record molecularsignals,primarily rotational transitions.…”

Section: Methodsmentioning

confidence: 99%

Unveiling the Sulfur–Sulfur Bridge: Accurate Structural and Energetic Characterization of a Homochalcogen Intermolecular Bond

et al. 2018

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By combining rotational spectroscopyinsupersonic expansion with the capability of state-of-the-art quantumchemical computations in accurately determining structural and energetic properties,the genuine nature of as ulfur-sulfur chalcogen bond between dimethyl sulfide and sulfur dioxide has been unveiled in agas-jet environment free from collision, solvent and matrix perturbations.ASAPT analysis pointed out that electrostatic S···S interactions play the dominant role in determining the stability of the complex, largely overcoming dispersion and CÀH···O hydrogen-bond contributions.Indeed, in agreement with the analysis of the quadrupole-coupling constants and of the methyl internal rotation barrier,the NBO and NOCV/CD approaches show am arked charge transfer between the sulfur atoms.B ased on the assignment of the rotational spectra for 7i sotopologues,a na ccurate semiexperimental equilibrium structure for the heavy-atom backbone of the molecular complex has been determined, whichis characterized by aS ···S distance (2.947(3) )w ell belowt he sum of van der Waals radii.

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Section: Methodsmentioning

confidence: 99%

Unveiling the Sulfur–Sulfur Bridge: Accurate Structural and Energetic Characterization of a Homochalcogen Intermolecular Bond

et al. 2018

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“…Crystalline samples of D-xylose (m.p. ¼ 162 C) have been vaporized by laser ablation and probed by CP-FTMW [222] using a new parabolic reflector system [268]. The recorded broadband spectrum, shown in Fig.…”

Section: -Deoxy-d-ribose and Ribosementioning

confidence: 99%

Microwave Spectroscopy of Biomolecular Building Blocks

Alonso

López

2014

Topics in Current Chemistry

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Microwave spectroscopy, considered as the most definitive gas phase structural probe, is able to distinguish between different conformational structures of a molecule, because they have unique spectroscopic constants and give rise to distinct individual rotational spectra.Previously, application of this technique was limited to molecular specimens possessing appreciable vapor pressures, thus discarding the possibility of studying many other molecules of biological importance, in particular those with high melting points, which had a tendency to undergo thermal reactions, and ultimately degradation, upon heating.Nowadays, the combination of laser ablation with Fourier transform microwave spectroscopy techniques, in supersonic jets, has enabled the gas-phase study of such systems. In this chapter, these techniques, including broadband spectroscopy, as well as results of their application into the study of the conformational panorama and structure of biomolecular building blocks, such as amino acids, nucleic bases, and monosaccharides, are briefly discussed, and with them, the tools for conformational assignation - rotational constants, nuclear quadrupole coupling interaction, and dipole moment.

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“…Hence, new high‐resolution spectroscopic techniques are gaining pivotal importance 20. In particular, the recent introduction of chirped‐excitation broadband microwave (MW) spectroscopy techniques21–23 offers broadband multiplexing capabilities and has dramatically expanded the molecular complexity amenable to rotational resolution studies 24. Here, we use a combination of supersonic‐jet techniques and broadband MW spectroscopy to examine the structural properties of the seven‐membered ring of ε‐caprolactone.…”

Section: Introductionmentioning

confidence: 99%

Pseudorotational Landscape of Seven‐Membered Rings: The Most Stable Chair and Twist‐Boat Conformers of ε‐Caprolactone

Jahn

Dewald

Vallejo‐López

et al. 2014

Chemistry A European J

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The conformational landscape and ring-puckering properties of ε-caprolactone have been analyzed by using microwave spectroscopy and quantum chemical calculations. Two conformers were detected in a supersonic jet expansion, the most stable form being a chair containing the ester group in its rectangular flap. This conformation benefits from reduced CH2 bond eclipsing and angle strain, while π-electron delocalization in the ester group is increased. The derived effective structure of the chair form satisfactorily agrees with the calculated near-equilibrium structure. A twist-boat conformer was also identified (9.4 kJ mol(-1) higher in energy at CCSD(T)/aug-cc-pVTZ level), and was located in the boat-twist-boat pseudorotation cycle of the seven-membered ring. Three other low-energy conformers were investigated and characterized in terms of the four puckering coordinates of the seven-membered ring. Potential interconversions in the four-dimensional conformation space are also discussed.

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Rapid capture of large amplitude motions in 2,6-difluorophenol: High-resolution fast-passage FT-MW technique

Cited by 35 publications

References 21 publications

Unveiling the Sulfur–Sulfur Bridge: Accurate Structural and Energetic Characterization of a Homochalcogen Intermolecular Bond

Unveiling the Sulfur–Sulfur Bridge: Accurate Structural and Energetic Characterization of a Homochalcogen Intermolecular Bond

Microwave Spectroscopy of Biomolecular Building Blocks

Pseudorotational Landscape of Seven‐Membered Rings: The Most Stable Chair and Twist‐Boat Conformers of ε‐Caprolactone

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