Rotational spectrum of chloroform, "grass-roots among the forest of trees": The v2 = 1, v3 = 2, v5 = 1, and v6 = 3 vibrational states of CH35Cl3. (December 2021)

• Record Type: Journal Article
• Authors: Ceausu-Velcescu, Adina; Pracna, Petr; Margules, Laurent; Predoi-Cross, Adriana
• Is Part Of: Journal of quantitative spectroscopy & radiative transfer. Volume 276(2021)
• Publication Date: 2021-12
• Subjects: Chloroform -- High-resolution MMW spectroscopy -- Excited vibrational states -- Difference band; Spectrum analysis -- Periodicals; Radiation -- Periodicals; Analyse spectrale -- Périodiques; Rayonnement -- Périodiques; Radiation; Spectrum analysis; Periodicals; 543.0858
• DOI: 10.1016/j.jqsrt.2021.107937
• Languages: English
• ISSNs: 0022-4073

Abstract

Highlights: First high-resolution rotational analysis of the v3 = 2, v2 = 1, and v5 = 1 levels of CH 35 Cl3 . First rovibrational analysis of the ν5 -ν6 difference band, near 515 cm −1 . Abstract: We have recently analyzed the broadband millimeter-wave rotational spectrum of chloroform CH 35 Cl3 in the v3 = v6 = 1 (E symmetry) and v6 = 2 (A1 + E ) excited vibrational states . In the present work, we have used the same spectrum (recorded in the 150 - 330 and 360–660 GHz spectral regions) for a rotational analysis of the v2 = 1 and v3 = 2 A1 states of the same molecule, together with a new analysis of the v5 =1 (E) fundamental vibration. For the v2 = 1 state (A1, near 677 cm −1 ), the body of assigned data comprises 392 rotational transitions. The corresponding frequencies were fitted within an isolated-level model, with a standard deviation of 36.4 kHz, and the obtained parameters are in good agreement with the previous IR work. For the v3 = 2 vibrational state (A1, near 734 cm −1 ), a total of 351 rotational transitions were assigned. Their fit was improved by inclusion of a second-order Coriolis coupling term with the v5 = 1 fundamental level, providing standard deviation of 40.2 kHz. At the same time, the description of the v5 = 1 vibration (E symmetry, 776 cm −1 ), studied previously with high-resolution as an isolated level, was also improved. The quantitative interpretation of the newly assigned 612 MMW data and the significantly extended set of IR assignments necessitated the introduction of the second-order Coriolis interaction with v3 = 2, but more importantly of an anharmonic interaction with the v6 = 3 (A1 + A2 + E, near 782 cm −1 ) level. For this latter level more than 200 rotational transitions, together with several series of rovibrational transitions, could finally be assigned and included in the fit. Graphical abstract: Image, graphical abstract