TY - JOUR
T1 - Revealing Internal Rotation and 14N Nuclear Quadrupole Coupling in the Atmospheric Pollutant 4-Methyl-2-nitrophenol
T2 - Interplay of Microwave Spectroscopy and Quantum Chemical Calculations
AU - Baweja, Shefali
AU - Antonelli, Eleonore
AU - Hussain, Safia
AU - Fernández-Ramos, Antonio
AU - Kleiner, Isabelle
AU - Nguyen, Ha Vinh Lam
AU - Sanz, M. Eugenia
N1 - Funding Information:
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).
Publisher Copyright:
© 2023 by the authors.
PY - 2023/3
Y1 - 2023/3
N2 - 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.
AB - 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.
KW - ab initio and density functional theory calculations
KW - internal rotation
KW - large-amplitude motion
KW - nuclear quadrupole coupling
KW - rotational spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85149828813&partnerID=8YFLogxK
U2 - 10.3390/molecules28052153
DO - 10.3390/molecules28052153
M3 - Article
C2 - 36903397
AN - SCOPUS:85149828813
SN - 1420-3049
VL - 28
JO - Molecules
JF - Molecules
IS - 5
M1 - 2153
ER -