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CE29 - Chimie : analyse, théorie, modélisation

Chirped Pulse And Resonator In one Spectrometer: A novel combined molecular jet chirped pulse/cavity Fourier Transform MicroWave spectrometer for fast scan, high-resolution, and chiral discrimination – PARIS-FTMW

Chirped pulse and resonator In one spectrometer: A novel combined molecular jet chirped pulse/cavity Fourier transform microwave spectrometer for fast scan, high-resolution, and chiral discrimination

The chirped Pulse And Resonator In one Spectrometer (PARIS) applies an innovative and resource-efficient approach: Using a smart design, most electronic components are used in a dual-purpose spectrometer while almost all vacuum equipment are shared. Therefore, PARIS is built at much lower costs than two individual spectrometers and exceeds the advantages of both techniques individually: Rapid broadband capabilities, intensity reliability, as well as unrivalled resolving power and sensitivity.

Development of a microwave spectrometer capable of high-sensitivity and high-resolution for spectral analysis, structure determination, and for three-wave mixing experiments for chiral analysis

The objective of the project is to develop a microwave spectrometer capable of high-sensitivity and high-resolution pure rotational spectroscopy for spectral analysis, structure determination, and for three-wave mixing experiments for chiral analysis. This apparatus combines a pulsed jet (narrow-band) resonator-type and a (broadband) chirped-pulse Fourier transform microwave spectrometer. Using a smart design, most electronic components will be used in a dual-purpose setup while all vacuum parts are identical. The two types of spectrometers are operated in either mode at no turn-around time. This highly integrated, innovative machine built at much lower costs yet offers the advantages of both techniques: Rapid broadband capabilities and unchallenged resolving power. <br /> <br />Enantiomer-specific detection by multiple resonance experiments is feasible with the spectrometer design. This instrument uses high frequency microwave pulses and applies this pulses in an optimal, time-separated pulse sequence, employing efficiently the nature of close-lying b- and c-type rotational transitions of a chiral molecule with the 1 GHz band-width of the chirped pulse in use. This will turn microwave spectroscopy into a powerful method for a routine application of chiral detections. <br /> <br />Studies on bio-active chiral molecules like odorant terpenes, pheromones, and complexes will be performed with chiral discrimination applications, yielding precise parameters of the molecular systems and the handedness of the molecules. This clearly integrates multidisciplinary aspects, especially for astronomy, Earth's atmosphere, and biology. The three molecular systems chosen are linalool, linalyl acetate, and the 1,2-propanediol--propylene oxide complex. All molecules are chiral and thus highlight the capability of PARIS-FTMW for chiral discrimination. Furthermore, they are flexible and floppy, therefore feature complex large amplitude motions which serve as tests for theoretical models and developments.

To build the PARIS spectrometer, an innovative and resource-efficient approach is applied: Using a smart design, most electronic components will be used in a dual-purpose spectrometer while almost all vacuum equipment are shared. The resonator-enhanced and chirp excitation spectrometers are combined in one single instrument, operated in either mode at no turn-around time.

The distinctive feature of PARIS-FTMW is that this setup is ideally suitable for the specific detection of chiral molecules. The narrow-banded resonator and the broadband horn antennas of the chirp setup will be mounted perpendicular to each other. The resonator can be tuned to a given frequency and plane of polarization. The horn antennas allow for simultaneous emission or reception of two identical or different frequencies at aligned or orthogonal polarization planes. Therefore, three independent frequencies and polarization planes are available, thereby allowing enantiomer-sensitive detection. The PARIS setup distinguished from other previously designed setups at the use of a Fabry-Perot resonator for creating one of the three polarizations, which has the advantage of power concentration in the resonator. Other setups use solely horn antennae instead.

A number of chiral molecules which serve as odorants or natural substances such as pheromones, where only one of the enantiomer features a scent or acts as the pheromone compound which releases reactions of insects, are the molecular target. The main aim of these studies will be their structural determination. The second goal is the analysis of large amplitude motions of these molecules, since such molecules are often flexible and floppy. This will serve as tests for theoretical models and developments.

The experimental axis of the first work package concerns the development of the PARIS spectrometer. Before the start of the project, the project coordinator (PI) began the purchase preparation (market research, update of offers from several companies, designation of mechanical components). As the total amount of major equipment was greater than € 144,000 H.T., a VISA request was performed with the CNRS to avoid a market research at European level. From 01.04.2019, components qualified as small equipment were ordered and delivered in 07.2019. For the purchase of large equipment, 3 PUMAs were published immediately after the start of the project. The two purchases concerning the electronic components were delivered at the end of 2019. For the mechanical components, consisting of a vacuum chamber and its accessories which were to be manufactured, the delivery date was initially 02.2020, but delayed to 07.2020 because of the COVID-19 crisis. The assembly was completed in 02.2021. For this task, the progress of the work is in accordance with the initial plan. The delay in the delivery of the vacuum chamber was compensated with the automatic extension of the project.

In parallel to the composition of the PARIS spectrometer, theoretical and spectral analysis studies were carried out. Since 03.2019, a master student has been recruited and participated in this work package. She pursued a PhD thesis and continues working on the tasks defined in this theoretical axis. The work progress on this axis matches very well the initial plan. During lockdown, when experimental work was not possible, the focus was placed on the theoretical axis of the project. The COVID crisis therefore had no impact; on the contrary, it allowed theoretical work to be accelerated with much more results than expected.

On the experimental axis, we entered the next workpackage concerning the test of the PARIS spectrometer after assembly. The main part is to test the operation of the vacuum and all mechanical parts.

On the theoretical axis, two tasks run in parallel. A task is on the development of the software to control and enable the interaction of all electronic components for recording the spectra. This task is mainly performed by the PI. The other task continues with theoretical studies and spectral analysis of target molecules, which is carried out jointly by the PI and the doctoral student.

Results of the project have been published in 25 peer-reviewed papers in ISI-ranked international scientific journals; two of them are review paper and a review paper was also published as a book chapter (H.V.L. Nguyen, I. Kleiner, DeGruyter, Ed. Gulaczyk, in press). Selected publications are given below.

1. H.V.L. Nguyen, Iwona Gulaczyk, Marek Kreglewski, I. Kleiner, Coord. Chem. Rev. 436, 213797 (2021).
Review article, Gold open access
2. J. Mélan, S. Khemissi, H.V.L. Nguyen, Spectro. Chim. Acta A 253, 119564 (2021).
3. H.V.L. Nguyen, M. Andresen, W. Stahl, Phys. Chem. Chem. Phys. 23, 2930 (2021).
4. H.V.L. Nguyen, I. Kleiner, Phys. Sci. Rev. (2021), in press.
Review article
5. M. Andresen, D. Schöngen, I. Kleiner, M. Schwell, W. Stahl, H.V.L. Nguyen, ChemPhysChem 21, 2206-2216 (2020).
6. S. Khemissi, H.V.L. Nguyen, ChemPhysChem 21, 1682-1687 (2020).
7. H.V.L. Nguyen, J.-U. Grabow, ChemPhysChem 21, 1243-1248 (2020).
Cover feature
8. S. Herbers, H.V.L. Nguyen, J. Mol. Spectrosc. 370, 111289 (2020).
9. T. Nguyen, V. Van, C. Gutlé, W. Stahl, M. Schwell, I. Kleiner, H.V.L. Nguyen, J. Chem. Phys. 152, 134306 (2020).
10. H.V.L. Nguyen, J. Mol. Struct. 1208, 127909 (2020).
11. L. Ferres, W. Stahl, H.V.L. Nguyen, J. Chem. Phys. 151, 104310 (2019).
Editor’s pick
12. M. Andresen, I. Kleiner, M. Schwell, W. Stahl, H.V.L. Nguyen, ChemPhysChem 20, 2063 (2019).
Cover feature

The results are also presented in 3 invited talks, an invited seminar of the PI, and a workshop organized by the PI (molecular spectroscopy days, Créteil/France, 2019). The most significant invited talk is a plenary lecture given at the internationally established conference “25th Colloquium on High resolution molecular spectroscopy” (2019) held in Dijon, France. The other two invited talks are at a workshop in Huelva/Spain (2019) and in Pisa/Italy (2019). The invited seminar was at Wesleyan/USA (2020, online).

The objective of the project is to develop a microwave spectrometer capable of high-sensitivity and high-resolution pure rotational spectroscopy for spectral analysis, structure determination, and for three-wave mixing experiments for chiral analysis. This novel apparatus called PARIS-FTMW combines a pulsed jet (narrow-band) resonator-type and a (broadband) chirped-pulse Fourier transform microwave spectrometer. Using a smart design, most electronic components will be used in a dual-purpose setup while all vacuum parts are identical. The two types of spectrometers are operated in either mode at no turn-around time. This highly integrated, innovative machine built at much lower costs yet offers the advantages of both techniques: Rapid broadband capabilities and unchallenged resolving power.
Enantiomer-specific detection by multiple resonance experiments is feasible with the spectrometer design. This instrument uses high frequency microwave pulses and applies this pulses in an optimal, time-separated pulse sequence, employing efficiently the nature of close-lying b- and c-type rotational transitions of a chiral molecule with the 1 GHz band-width of the chirped pulse in use. Chiral discrimination is currently not a standard method in microwave spectroscopy. PARIS-FTMW with its flexibility in configuration changes will turn high resolution microwave spectroscopy into a powerful method for a routine application of chiral detections.
Studies on bio-active chiral molecules like odorant terpenes, pheromones, and complexes will be performed with chiral discrimination applications, yielding precise parameters of the molecular systems and the handedness of the molecules. This clearly integrates multidisciplinary aspects, especially for astronomy, Earth's atmosphere, and biology. The three molecular systems chosen are linalool, linalyl acetate, and the 1,2-propanediol--propylene oxide complex. All molecules are chiral and thus highlight the capability of PARIS-FTMW for chiral discrimination. Furthermore, they are flexible and floppy, therefore feature complex large amplitude motions which serve as tests for theoretical models and developments.

Project coordinator

Madame Ha Vinh Lam Nguyen (Laboratoire interuniversitaire des systèmes atmosphériques)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

LISA Laboratoire interuniversitaire des systèmes atmosphériques

Help of the ANR 461,328 euros
Beginning and duration of the scientific project: March 2019 - 42 Months

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