Millimeter-Wave and High-Resolution Infrared Spectroscopy of the Ground and Seven Lowest Fundamental States of 1H‑1,2,4-Triazole

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 128; no. 33; pp. 6927 - 6942
• Main Authors: Bunn, Hayley A., Zdanovskaia, Maria A., Billinghurst, Brant E., Zhao, Jianbao, Widicus Weaver, Susanna L., Woods, R. Claude, McMahon, Robert J., Esselman, Brian J.
• Format: Journal Article
• Language: English
• Published: American Chemical Society 22.08.2024
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c03890

A combined analysis of millimeter-wave (70–700 GHz) and rotationally resolved infrared (400–1200 cm–1) spectra of the ground state and seven fundamental vibrational modes of 1H-1,2,4-triazole is reported. While the lowest-energy vibrationally excited state (ν18) is well-treated using a single-state distorted-rotor Hamiltonian, the second (ν17) and third (ν16) vibrationally excited states are involved in strong c-type Coriolis coupling and require an appropriate two-state Hamiltonian. The oblate nature of 1H-1,2,4-triazole is sufficiently close to the oblate symmetric-top limit that the analysis requires the use of A-reduced, sextic centrifugally distorted-rotor Hamiltonian models in the I r representation in order to achieve low σfit values. The coupling between ν17 (A″) and ν16 (A″) resulted in many transitions with slightly perturbed frequencies, many highly displaced resonant intrastate transitions, and 165 nominal interstate transitions. Modeling the spectra of ν17 and ν16 required three c-axis Coriolis-coupling terms (F ab , F ab J , and F ab K ) to treat the interaction. Many of the nominal interstate transitions form clearly discernible Q-branch bands, comprising degenerate sets of a- and b-type transitions. The rotational spectra of four higher-energy vibrationally excited states (ν15, ν14, ν13, and ν12), which form a complex polyad involving Coriolis and anharmonic coupling interactions, were analyzed by single-state models, thus producing only effective spectroscopic constants. Inclusion of rotationally resolved infrared transitions enabled the accurate and precise determination of vibrational band origins for the four lowest-energy fundamental states: ν18 = 542.601 824 3 (28) cm–1, ν17 = 665.183 128 5 (43) cm–1, ν16 = 682.256 910 5 (43) cm–1, and ν15 = 847.557 400 (11) cm–1.