Exploring low barrier quantum tunneling and structural planarity in 3-methylstyrene conformers: Insights from microwave spectroscopy

Abstract

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.