Revealing Internal Rotation and 14N Nuclear Quadrupole Coupling in the Atmospheric Pollutant 4-Methyl-2-nitrophenol: Interplay of Microwave Spectroscopy and Quantum Chemical Calculations

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URI: https://hdl.handle.net/10347/38247
ISSN: 1420-3049
DOI: 10.3390/molecules28052153

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2023-02-24

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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.

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Rotational spectroscopy| Ab initio and density functional theory calculations| Internal rotation| Nuclear quadrupole coupling| Large-amplitude motio

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Baweja, S., Antonelli, E., Hussain, S., Fernández-Ramos, A., Kleiner, I., Nguyen, H.V.L., Sanz, M.E.(2023). Revealing Internal Rotation and 14N Nuclear Quadrupole Coupling in the Atmospheric Pollutant 4-Methyl-2-nitrophenol: Interplay of Microwave Spectroscopy and Quantum Chemical Calculations. “Molecules”, vol. 28(5). https:// doi.org/10.3390/molecules28052153

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This research was funded by the Université de Paris–King’s College London Joint Research Award and was co-funded by the Agence Nationale de la Recherche (ANR, grant number ANR-18-CE29-0011), by the European Union (ERC grant 101040480-LACRIDO, and PCIG12-GA-2012-334525), and Ministerio de Ciencia e Innovación (grant PID2019-107307RB-I00). S.B. thanks King’s College London for a PGR International Scholarship. We acknowledge use of the research computing facilities at King’s College London, Rosalind (https://rosalind.kcl.ac.uk) and CREATE (King’s Computational Research, Engineering and Technology Environment. https://doi.org/10.18742/rnvf-m076, accessed on 31 January 2023).

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© 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).
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Química Física
Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)