The first ground-state rotational spectrum of 3-methylstyrene (3MS) was measured by Fourier transform microwave spectroscopy under supersonic jet-cooled conditions. Transitions were assigned for two conformers: cis-3MS and trans-3MS. In the cis conformer, the vinyl group is oriented toward the methyl group, while in the trans conformer, it is positioned away from the methyl. The energy difference between the two conformers was calculated to be only 2.1 cm−1, with the cis conformer having lower energy. Significant tunneling splitting, caused by the low-barrier internal rotation of the methyl group, was observed and analyzed using the XIAM and BELGI-Cs codes. The BELGI results show that the V3 barrier is 30.6688(87) cm−1 for the cis conformer and 11.0388(88) cm−1 for the trans conformer. The experimental rotational and torsional parameters are compared to their density functional theory counterparts. The planarity of the molecular geometry of cis- and trans-3MS is discussed, contributing to the long-standing topic of discussion about the planarity of styrene derivatives.
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Exploring low barrier quantum tunneling and structural planarity in 3-methylstyrene conformers: Insights from microwave spectroscopy
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28 January 2025
Research Article|
January 22 2025
Exploring low barrier quantum tunneling and structural planarity in 3-methylstyrene conformers: Insights from microwave spectroscopy
Special Collection:
2024 JCP Emerging Investigators Special Collection
Thusitha S. Jayasekara
;
Thusitha S. Jayasekara
(Formal analysis, Investigation, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, Tennessee Tech University
, Cookeville, Tennessee 38505, USA
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Cadence Miller
;
Cadence Miller
(Formal analysis, Writing – review & editing)
1
Department of Chemistry, Tennessee Tech University
, Cookeville, Tennessee 38505, USA
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Dinesh Marasinghe;
Dinesh Marasinghe
(Investigation)
2
Department of Chemistry and Biochemistry, Kent State University
, Kent, Ohio 44242, USA
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Michael J. Carrillo
;
Michael J. Carrillo
(Investigation)
2
Department of Chemistry and Biochemistry, Kent State University
, Kent, Ohio 44242, USA
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Mitchell Swann
;
Mitchell Swann
(Investigation)
1
Department of Chemistry, Tennessee Tech University
, Cookeville, Tennessee 38505, USA
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Michael J. Tubergen
;
Michael J. Tubergen
(Investigation, Writing – review & editing)
2
Department of Chemistry and Biochemistry, Kent State University
, Kent, Ohio 44242, USA
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Isabelle Kleiner
;
Isabelle Kleiner
(Formal analysis, Writing – review & editing)
3
Université Paris Cité and Univ Paris Est Creteil, CNRS, LISA
, F-75013 Paris, France
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Ranil M. Gurusinghe
Ranil M. Gurusinghe
a)
(Conceptualization, Formal analysis, Funding acquisition, Investigation, Project administration, Supervision, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, Tennessee Tech University
, Cookeville, Tennessee 38505, USA
a)Author to whom correspondence should be addressed: [email protected]. Telephone: 931-372-6849
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a)Author to whom correspondence should be addressed: [email protected]. Telephone: 931-372-6849
J. Chem. Phys. 162, 044303 (2025)
Article history
Received:
September 10 2024
Accepted:
November 19 2024
Citation
Thusitha S. Jayasekara, Cadence Miller, Dinesh Marasinghe, Michael J. Carrillo, Mitchell Swann, Michael J. Tubergen, Isabelle Kleiner, Ranil M. Gurusinghe; Exploring low barrier quantum tunneling and structural planarity in 3-methylstyrene conformers: Insights from microwave spectroscopy. J. Chem. Phys. 28 January 2025; 162 (4): 044303. https://doi.org/10.1063/5.0238251
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