Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave Spectroscopy

The microwave spectrum of 3,5-dimethylanisole was recorded using a pulsed molecular jet Fourier transform microwave spectrometer, covering the frequency range from 2.0 to 26.5 GHz. Splittings from internal rotations of the <i>syn</i>-<i>m</i> and <i>anti</i>-<i...

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Main Authors: Safa Khemissi, Lynn Ferres, Ha Vinh Lam Nguyen
Format: Article
Language:English
Published: MDPI AG 2025-03-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/6/1195
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author Safa Khemissi
Lynn Ferres
Ha Vinh Lam Nguyen
author_facet Safa Khemissi
Lynn Ferres
Ha Vinh Lam Nguyen
author_sort Safa Khemissi
collection DOAJ
description The microwave spectrum of 3,5-dimethylanisole was recorded using a pulsed molecular jet Fourier transform microwave spectrometer, covering the frequency range from 2.0 to 26.5 GHz. Splittings from internal rotations of the <i>syn</i>-<i>m</i> and <i>anti</i>-<i>m</i>-methyl groups were observed, analyzed, and modeled using the <i>XIAM</i> and the <i>ntop</i> programs for a data set including 622 rotational lines. The torsional barriers of the <i>syn</i>-<i>m</i> and <i>anti</i>-<i>m</i>-methyl groups were determined to be 58.62367(53) cm<sup>−1</sup> and 36.28449(69) cm<sup>−1</sup>, respectively. The low barriers to internal rotation of both methyl groups posed significant challenges for spectral analysis and modeling. The successful assignment was achieved using combination difference loops and separately fitting the five torsional components. Comparing the torsional barriers observed in various toluene derivatives with methyl groups at <i>meta</i>-positions supports the assumption that electrostatic effects contribute more significantly than steric effects in the low-barrier cases of aromatic molecules.
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spelling doaj-art-d22ad6451b43453d8da089c4645295652025-08-20T02:42:22ZengMDPI AGMolecules1420-30492025-03-01306119510.3390/molecules30061195Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave SpectroscopySafa Khemissi0Lynn Ferres1Ha Vinh Lam Nguyen2Univ Paris Est Créteil and Université Paris Cité, CNRS, LISA, F-94010 Créteil, FranceInstitute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074 Aachen, GermanyUniv Paris Est Créteil and Université Paris Cité, CNRS, LISA, F-94010 Créteil, FranceThe microwave spectrum of 3,5-dimethylanisole was recorded using a pulsed molecular jet Fourier transform microwave spectrometer, covering the frequency range from 2.0 to 26.5 GHz. Splittings from internal rotations of the <i>syn</i>-<i>m</i> and <i>anti</i>-<i>m</i>-methyl groups were observed, analyzed, and modeled using the <i>XIAM</i> and the <i>ntop</i> programs for a data set including 622 rotational lines. The torsional barriers of the <i>syn</i>-<i>m</i> and <i>anti</i>-<i>m</i>-methyl groups were determined to be 58.62367(53) cm<sup>−1</sup> and 36.28449(69) cm<sup>−1</sup>, respectively. The low barriers to internal rotation of both methyl groups posed significant challenges for spectral analysis and modeling. The successful assignment was achieved using combination difference loops and separately fitting the five torsional components. Comparing the torsional barriers observed in various toluene derivatives with methyl groups at <i>meta</i>-positions supports the assumption that electrostatic effects contribute more significantly than steric effects in the low-barrier cases of aromatic molecules.https://www.mdpi.com/1420-3049/30/6/1195microwave spectroscopylarge amplitude motionsinternal rotationlow barriers
spellingShingle Safa Khemissi
Lynn Ferres
Ha Vinh Lam Nguyen
Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave Spectroscopy
Molecules
microwave spectroscopy
large amplitude motions
internal rotation
low barriers
title Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave Spectroscopy
title_full Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave Spectroscopy
title_fullStr Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave Spectroscopy
title_full_unstemmed Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave Spectroscopy
title_short Two Coupled Low-Barrier Large Amplitude Motions in 3,5-Dimethylanisole Studied by Microwave Spectroscopy
title_sort two coupled low barrier large amplitude motions in 3 5 dimethylanisole studied by microwave spectroscopy
topic microwave spectroscopy
large amplitude motions
internal rotation
low barriers
url https://www.mdpi.com/1420-3049/30/6/1195
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AT lynnferres twocoupledlowbarrierlargeamplitudemotionsin35dimethylanisolestudiedbymicrowavespectroscopy
AT havinhlamnguyen twocoupledlowbarrierlargeamplitudemotionsin35dimethylanisolestudiedbymicrowavespectroscopy