Two-dimensional (2D) correlation techniques are developed for chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. The broadband nature of the spectrometer coupled with fast digital electronics permits the generation of arbitrary pulse sequences and simultaneous detection of the 8-18 GHz region of the microwave spectrum. This significantly increases the number of rotation transitions that can be simultaneously probed, as well as the bandwidth in both frequency dimensions. We theoretically and experimentally evaluate coherence transfer of three- and four-level systems to relate the method with previous studies. We then extend the principles of single-quantum and autocorrelation to incorporate broadband excitation and detection. Global connectivity of the rotational energy level structure is demonstrated through the transfer of multiple coherences in a single 2D experiment. Additionally, open-system effects are observed from irradiating many-level systems. Quadrature detection in the indirectly measured frequency dimension and phase cycling are also adapted for 2D CP-FTMW spectroscopy.
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http://dx.doi.org/10.1021/jp2043202 | DOI Listing |
Phys Chem Chem Phys
January 2025
Purchase College SUNY, School of Natural and Social Sciences, 735 Anderson Hill Rd, Purchase, NY, 10577, USA.
For the first time, rotational constants along with centrifugal distortion constants have been determined for OThS and OCeS. The rotational spectra of these molecules and, in each case, one other isotopologue (OThS and OCeS) were produced utilizing a laser ablation sourcing technique incorporated into a chirped-pulse Fourier transform microwave spectrometer operating in the 8 to 18 GHz region of the electromagnetic spectrum. The bent structures determined are in very good agreement with theoretical calculations.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias─I.U. CINQUIMA, Paseo de Belén, 7, 47011 Valladolid, Spain.
The conformational space of 3-chloropropionic acid has been studied under the isolated conditions of a supersonic expansion using Stark-modulated free-jet absorption millimeter-wave and centimeter-wave chirped-pulse Fourier transform microwave spectroscopy techniques. The rotational spectra originating from the three most stable conformers including Cl and Cl isotopologues were observed in both experiments using helium expansion while a partial conformational relaxation involving skeletal rearrangements takes place in an argon expansion. The rotational parameters, geometries, and energy order were determined from the experiment, allowing a comparison with quantum chemical predictions.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.
The rotational spectra of a mixture of 2,4-pentanediol (PDL) isomers, comprising both the meso isomers [(2R, 4S) and (2S, 4R)] and the racemic isomers [(2R, 4R) and (2S, 4S)], were recorded using a chirped-pulse Fourier transform microwave spectrometer coupled to a supersonic jet expansion. The conformational landscapes of meso- and racemic-PDL were examined using the Conformer-Rotamer Ensemble Sampling Tool and high-level quantum chemical calculations, generating 26 and 25 conformers, respectively. Five sets of rotational transitions were observed and assigned, with two attributed to meso-PDL and the remaining three attributed to racemic-PDL.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.
Criegee intermediates (CIs) play an important role in atmospheric chemistry as a transient source of the OH radical through their formation by the ozonolysis of unsaturated organic compounds. Here, we report thermally initiated formation of the smallest CI (CHOO) in the oxidation of ethane (CHCH) that may be relevant to combustion and flames. The SiO/SiC oxidation microreactor is heated to 1800 K and has a short residence time of ∼100 μs.
View Article and Find Full Text PDFIn situ characterization of the electric field of ultrafast pulses is critical in multiphoton microscopy. Although second harmonic generation-based collinear Frequency-Resolved Optical Gating (FROG) addresses this need, the interferometric measurement is challenged by interferometric drift instability, the required high sampling density of the acquired data, and the inability to directly use the interferometric data with conventional FROG retrieval algorithms. We address these issues by combining low-pass Fourier filtering with active kHz dithering of the interferometric path length difference using a piezo-driven retroreflector.
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