Rotational Spectroscopy of 1‑Cyano-2-methylenecyclopropane (C5H5N)A Newly Synthesized Pyridine Isomer

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 128; no. 8; pp. 1427 - 1437
• Main Authors: Jean, Dairen R., Wood, Samuel A., Esselman, Brian J., Woods, R. Claude, McMahon, Robert J.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 29-02-2024
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c08002

The gas-phase rotational spectrum of 1-cyano-2-methylenecyclopropane (C 1, C5H5N), an isomer of pyridine, is presented for the first time, covering the range from 235 to 500 GHz. Over 3600 a-, b-, and c-type transitions for the ground vibrational state have been assigned, measured, and least-squares fit to partial-octic A- and S-reduced distorted-rotor Hamiltonians with low statistical uncertainty (σfit = 42 kHz). Transitions for the two lowest-energy fundamental states (ν27 and ν26) and the lowest-energy overtone (2ν27) have been similarly measured, assigned, and least-squares fit to single-state Hamiltonians. Computed vibration–rotation interaction constants (B 0–B v ) using the B3LYP and MP2 levels of theory are compared with the corresponding experimental values. Based upon our preliminary analysis, the next few vibrationally excited states form one or more complex polyads of interacting states via Coriolis and anharmonic coupling. The spectroscopic constants and transition frequencies presented here form the foundation for both future laboratory spectroscopy and astronomical searches for 1-cyano-2-methylenecyclopropane.