ROTATIONAL SPECTRUM OF CH$_2$FI FROM 5 GHZ UP TO 1 THZ: ACCURATE SPECTROSCOPIC AND HYPERFINE PARAMETERS
Lopez, Juan Carlos
Alonso, Jose Luis
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Publisher:Ohio State University
Guided by theoretical predictions, the rotational spectrum of fluoroiodomethane, CH$_2$FI, has been been recorded and assigned. Three different spectrometers have been employed, a Fourier Transform Microwave spectrometer, a Millimeter-/Submillimeter- wave Spectrometer, and a THz spectrometer, thus allowing to record a huge portion of the rotational spectrum, from 5 GHz up to 1 THz, and to accurately determine the ground-state rotational and centrifugal-distortion constants. The hyperfine structure of the rotational spectrum has been investigated by means of the Fourier Transform Microwave spectrometer and the Lamb-dip technique in the millimeter-/submillimeter-wave region, thus allowing the determination of the complete iodine quadrupole-coupling tensor and of the diagonal elements of the iodine spin-rotation tensor. Regarding the quantum-chemical calculations, inclusion of relativistic effects turned out to be essential for obtaining reliable and quantitative predictions for experiment, and they have been accounted for either by means of second-order direct perturbation theory or via a spin-free approach based on the Dirac Coulomb Hamiltonian, both in combination with coupled-cluster techniques to treat electron correlation and sufficiently large basis sets.
Author Institution: Dipartimento di Chimica "G. Ciamician", Universita di Bologna, I-40126 Bologna, Italy; Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, E-47005, Valladolid, Spain; Dipartimento di Chimica Fisica, Universita "Ca' Foscari'' Venezia, D.D. 2137, I-30123 Venezia, Italy; Institut fur Physikalische Chemie, Universitat Mainz, D-55099 Mainz, Germany