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

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...

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Bibliographic Details
Authors: Baweja, Shefali, Antonelli, Eleonore, Hussain, Safia, Fernández Ramos, Antonio, Kleiner, Isabelle, Sanz, M. Eugenia, Nguyen, Ha Vinh Lam
Format: article
Publication Date:2023
Country:España
Institution:Universidad de Santiago de Compostela (USC)
Repository:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
Language:English
OAI Identifier:oai:minerva.usc.gal:10347/38247
Online Access:https://hdl.handle.net/10347/38247
Access Level:Open access
Keyword:Rotational spectroscopy
Ab initio and density functional theory calculations
Internal rotation
Nuclear quadrupole coupling
Large-amplitude motio
2391 Química ambiental
Description
Summary: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.