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The Interplay between Spectroscopy and Quantum Chemistry for Environment: From Atmospheric Monitoring to Climate Changes

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Cross-Field Chemistry".

Deadline for manuscript submissions: closed (31 July 2023) | Viewed by 11076

Special Issue Editors


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Guest Editor
SMART Lab, Scuola Normale Superiore, Piazza dei Cavalieri 7, I-56126 Pisa, Italy
Interests: quantum chemistry; infrared spectroscopy; rotational-vibrational spectroscopy; atmospheric chemistry; astrochemistry

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Guest Editor
Laboratoire Interdisciplinaire Carnot de Bourgogne, 9 avenue Alain Savary, BP 47870, CEDEX, 21078 Dijon, France
Interests: molecular physics; high-resolution absorption and Raman spectroscopy; theoretical developments in molecular spectroscopy; modeling of high-resolution spectra: CH4, CF4, SF6, GeH4, SiF4, RuO4, C2H4, …; molecular spectroscopy databases; applications to atmospheric and climate sciences; greenhouse gases; applications to the atmospheres of planets and exoplanets

Special Issue Information

Composition changes of the Earth’s atmosphere, mainly due to various anthropogenic factors occurring in the last decades, are considered responsible for several adverse climate and environmental impacts. Since the industrial revolution, anthropogenic activities have exerted a profound impact on the atmospheric composition, both altering the mixing ratio of natural occurring gases and releasing synthetic hazardous chemicals. Climate change studies need the temporal trend of hazardous atmospheric pollutants of both greenhouse and ozone-depleting gases. For this purpose, remote sensing spectroscopic techniques are widely used to probe the atmosphere and retrieve the concentration profiles of a number of species. Besides environmental monitoring, the fate of the compounds released into the atmosphere needs to be precisely characterized in order to understand how rapidly these substances degrade, when and where they are destroyed, and whether the degradation products can lead to more climate forcing than the parent species.

Understanding all these aspects is far from a simple task, which, in order to be accomplished, requires the synergic interplay between spectroscopy experiments and accurate quantum chemical simulations. This Special Issue aims to collect both spectroscopic experimental investigations and theoretical simulations devoted to the characterization of molecules’ spectroscopic features for atmospheric monitoring, and the atmospheric degradation pathways.

Dr. Nicola Tasinato
Dr. Vincent Boudon

Guest Editors

Manuscript Submission Information

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Keywords

  • Molecular spectroscopy
  • Quantum mechanical calculations
  • Atmospheric reactivity
  • Chemical kinetics
  • Spectroscopic parameters
  • Ozone-depleting substances
  • Greenhouse gases

Published Papers (5 papers)

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Research

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21 pages, 2925 KiB  
Article
Rovibrational Spectroscopy of Trans and Cis Conformers of 2-Furfural from High-Resolution Fourier Transform and QCL Infrared Measurements
by Sathapana Chawananon, Pierre Asselin, Jordan A. Claus, Manuel Goubet, Anthony Roucou, Robert Georges, Joanna Sobczuk, Colwyn Bracquart, Olivier Pirali and Arnaud Cuisset
Molecules 2023, 28(10), 4165; https://doi.org/10.3390/molecules28104165 - 18 May 2023
Viewed by 1070
Abstract
The ortho-isomer 2-furfural (2-FF), which is a primary atmospheric pollutant produced from biomass combustion, is also involved in oxidation processes leading to the formation of secondary organic aerosols. Its contribution to radiative forcing remains poorly understood. Thus, monitoring 2-FF directly in the atmosphere [...] Read more.
The ortho-isomer 2-furfural (2-FF), which is a primary atmospheric pollutant produced from biomass combustion, is also involved in oxidation processes leading to the formation of secondary organic aerosols. Its contribution to radiative forcing remains poorly understood. Thus, monitoring 2-FF directly in the atmosphere or in atmospheric simulation chambers to characterize its reactivity is merited. The present study reports an extensive jet-cooled rovibrational study of trans and cis conformers of 2-FF in the mid-IR region using two complementary setups: a continuous supersonic jet coupled to a high-resolution Fourier transform spectrometer on the IR beamline of the SOLEIL synchrotron (JET-AILES), and a pulsed jet coupled to a mid-IR tunable quantum cascade laser spectrometer (SPIRALES). Firstly, jet-cooled spectra recorded at rotational temperatures ranging between 20 and 50 K were exploited to derive reliable excited-state molecular parameters of trans- and cis-2-FF vibrational bands in the fingerprint region. The parameters were obtained from global fits of 11,376 and 3355 lines distributed over eight and three vibrational states (including the ground state), respectively, with a root mean square of 12 MHz. In a second step, the middle resolution spectrum of 2-FF recorded at 298.15 K and available in the HITRAN database was reconstructed by extrapolating the data derived from our low-temperature high-resolution analyses to determine the cross sections of each vibrational band of both 2-FF conformers in the 700–1800 cm−1 region. Finally, we clearly demonstrated that the contribution of hot bands observed in the room temperature 2-FF spectrum, estimated between 40 and 63% of the fundamental band, must be imperatively introduced in our simulation to correctly reproduce the HITRAN vibrational cross sections of 2-FF with a deviation smaller than 10%. Full article
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13 pages, 2124 KiB  
Article
Revealing Internal Rotation and 14N Nuclear Quadrupole Coupling in the Atmospheric Pollutant 4-Methyl-2-nitrophenol: Interplay of Microwave Spectroscopy and Quantum Chemical Calculations
by Shefali Baweja, Eleonore Antonelli, Safia Hussain, Antonio Fernández-Ramos, Isabelle Kleiner, Ha Vinh Lam Nguyen and M. Eugenia Sanz
Molecules 2023, 28(5), 2153; https://doi.org/10.3390/molecules28052153 - 24 Feb 2023
Cited by 3 | Viewed by 1564
Abstract
The structure and interactions of oxygenated aromatic molecules are of atmospheric interest due to their toxicity and as precursors of aerosols. Here, we present the analysis of 4-methyl-2-nitrophenol (4MNP) using chirped pulse and Fabry–Pérot Fourier transform microwave spectroscopy in combination with quantum chemical [...] Read more.
The structure and interactions of oxygenated aromatic molecules are of atmospheric interest due to their toxicity and as precursors of aerosols. Here, we present the analysis of 4-methyl-2-nitrophenol (4MNP) using chirped pulse and Fabry–Pérot Fourier transform microwave spectroscopy in combination with quantum chemical calculations. The rotational, centrifugal distortion, and 14N nuclear quadrupole coupling constants of the lowest-energy conformer of 4MNP were determined as well as the barrier to methyl internal rotation. The latter has a value of 106.4456(8) cm−1, significantly larger than those from related molecules with only one hydroxyl or nitro substituent in the same para or meta positions, respectively, as 4MNP. Our results serve as a basis to understand the interactions of 4MNP with atmospheric molecules and the influence of the electronic environment on methyl internal rotation barrier heights. Full article
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22 pages, 671 KiB  
Article
The Spectroscopic Characterization of Halogenated Pollutants through the Interplay between Theory and Experiment: Application to R1122
by Andrea Pietropolli Charmet, Giorgia Ceselin, Paolo Stoppa and Nicola Tasinato
Molecules 2022, 27(3), 748; https://doi.org/10.3390/molecules27030748 - 24 Jan 2022
Cited by 8 | Viewed by 2474
Abstract
In the last decade, halogenated ethenes have seen an increasing interest for different applications; in particular, in refrigeration, air-conditioning and heat pumping. At the same time, their adverse effects as atmospheric pollutants require environmental monitoring, especially by remote sensing spectroscopic techniques. For this [...] Read more.
In the last decade, halogenated ethenes have seen an increasing interest for different applications; in particular, in refrigeration, air-conditioning and heat pumping. At the same time, their adverse effects as atmospheric pollutants require environmental monitoring, especially by remote sensing spectroscopic techniques. For this purpose, an accurate characterization of the spectroscopic fingerprint—in particular, those of relevance for rotational–vibrational spectroscopy—of the target molecules is strongly needed. This work provides an integrated computational–theoretical investigation on R1122 (2-Chloro-1,1-difluoro-ethylene, ClHC=CF2), a compound widely employed as a key intermediate in different chemical processes. State-of-the-art quantum chemical calculations relying on CCSD(T)-based composite schemes and hybrid CCSD(T)/DFT approaches are used to obtain an accurate prediction of the structural, rotational and vibrational spectroscopic properties. In addition, the equilibrium geometry is obtained by exploiting the semi-experimental method. The theoretical predictions are used to guide the analysis of the experimentally recorded gas-phase infrared spectrum, which is assigned in the 400–6500 cm1 region. Furthermore, absorption cross sections are accurately determined over the same spectral range. Finally, by using the obtained spectroscopic data, a first estimate of the global warming potential of R1122 vibrational spectra is obtained. Full article
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12 pages, 4546 KiB  
Article
Nitrogen-Broadening Parameters for Atmospheric Spectra Modelling of the ν3 Band of SF6
by Nawel Dridi, Vincent Boudon, Mbaye Faye and Laurent Manceron
Molecules 2022, 27(3), 646; https://doi.org/10.3390/molecules27030646 - 19 Jan 2022
Cited by 2 | Viewed by 1298
Abstract
The infrared absorption of the ν3 band region of SF6, at temperatures spanning the 130 to 297 K range, has been reexamined using improved instrumentation with one goal: to estimate the broadening of parameters by nitrogen gas. These parameters are compared [...] Read more.
The infrared absorption of the ν3 band region of SF6, at temperatures spanning the 130 to 297 K range, has been reexamined using improved instrumentation with one goal: to estimate the broadening of parameters by nitrogen gas. These parameters are compared to previous literature predictions and an extended set of IR cross-sections is proposed and compared to other existing datasets. Full article
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Review

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51 pages, 9120 KiB  
Review
High Resolution Infrared Spectroscopy in Support of Ozone Atmospheric Monitoring and Validation of the Potential Energy Function
by Alain Barbe, Semen Mikhailenko, Evgeniya Starikova and Vladimir Tyuterev
Molecules 2022, 27(3), 911; https://doi.org/10.3390/molecules27030911 - 28 Jan 2022
Cited by 9 | Viewed by 3664
Abstract
The first part of this review is a brief reminder of general information concerning atmospheric ozone, particularly related to its formation, destruction, observations of its decrease in the stratosphere, and its increase in the troposphere as a result of anthropogenic actions and solutions. [...] Read more.
The first part of this review is a brief reminder of general information concerning atmospheric ozone, particularly related to its formation, destruction, observations of its decrease in the stratosphere, and its increase in the troposphere as a result of anthropogenic actions and solutions. A few words are said about the abandonment of the Airbus project Alliance, which was expected to be the substitute of the supersonic Concorde. This project is over due to the theoretical evaluation of the impact of a fleet in the stratosphere and has been replaced by the A380, which is now operating. The largest part is devoted to calculations and observations of the transitions in the infrared range and their applications for the atmosphere based both on effective models (Hamiltonian, symmetry rules, and dipole moments) and ab initio calculations. The complementarities of the two approaches are clearly demonstrated, particularly for the creation of an exhaustive line list consisting of more than 300,000 lines reaching experimental accuracies (from 0.00004 to 0.001 cm−1) for positions and a sub percent for the intensities in the 10 microns region. This contributes to definitively resolving the issue of the observed discrepancies between line intensity data in different spectral regions: between the infrared and ultraviolet ranges, on the one hand, and between 10 and 5 microns on the other hand. The following section is devoted to the application of recent work to improve the knowledge about the behavior of potential function at high energies. A controversial issue related to the shape of the potential function in the transition state range near the dissociation is discussed. Full article
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