Very short-lived substances have recently been proposed as replacements for hydrofluorocarbons (HFCs), in turn being used in place of ozone-depleting substances, in refrigerant applications. In this respect, hydro-fluoro-olefins (HFOs) are attracting particular interest because, due to their reduced global warming potential, they are supposed to be environmentally friendlier. Notwithstanding this feature, they represent a new class of compounds whose spectroscopic properties and reactivity need to be characterized to allow their atmospheric monitoring and to understand their environmental fate. In the present work, the structural, vibrational, and ro-vibrational properties of trifluorothene (HFO-1123, F2C = CHF) are studied by state-of-the-art quantum chemical calculations. The equilibrium molecular structure has an expected error within 2 mÅ and 0.2° for bond lengths and angles, respectively. This represents the first step toward the computation of highly accurate rotational constants for both the ground and first excited fundamental vibrational levels, which reproduce the available experimental data well within 0.1%. Centrifugal distortion parameters and vibrational-rotational coupling terms are computed as well and used to solve some conflicting experimental results. Simulation of the vibrational transition frequencies and intensities beyond the double harmonic approximation and up to three quanta of vibrational excitation provides insights into the couplings ruling the vibrational dynamics and guides the characterization of the gas-phase infrared spectrum experimentally recorded in the range of 200-5000 cm-1. The full characterization of the IR features is completed with the experimental determination of the absorption cross sections over the 400-5000 cm-1 region from which the radiative forcing and global warming potential of HFO-1123 are derived.

In vitro and in silico vibrational-rotational spectroscopic characterization of the next-generation refrigerant HFO-1123

Tasinato, Nicola
;
Ceselin, Giorgia;Salta, Zoi;
2022

Abstract

Very short-lived substances have recently been proposed as replacements for hydrofluorocarbons (HFCs), in turn being used in place of ozone-depleting substances, in refrigerant applications. In this respect, hydro-fluoro-olefins (HFOs) are attracting particular interest because, due to their reduced global warming potential, they are supposed to be environmentally friendlier. Notwithstanding this feature, they represent a new class of compounds whose spectroscopic properties and reactivity need to be characterized to allow their atmospheric monitoring and to understand their environmental fate. In the present work, the structural, vibrational, and ro-vibrational properties of trifluorothene (HFO-1123, F2C = CHF) are studied by state-of-the-art quantum chemical calculations. The equilibrium molecular structure has an expected error within 2 mÅ and 0.2° for bond lengths and angles, respectively. This represents the first step toward the computation of highly accurate rotational constants for both the ground and first excited fundamental vibrational levels, which reproduce the available experimental data well within 0.1%. Centrifugal distortion parameters and vibrational-rotational coupling terms are computed as well and used to solve some conflicting experimental results. Simulation of the vibrational transition frequencies and intensities beyond the double harmonic approximation and up to three quanta of vibrational excitation provides insights into the couplings ruling the vibrational dynamics and guides the characterization of the gas-phase infrared spectrum experimentally recorded in the range of 200-5000 cm-1. The full characterization of the IR features is completed with the experimental determination of the absorption cross sections over the 400-5000 cm-1 region from which the radiative forcing and global warming potential of HFO-1123 are derived.
Settore CHIM/12 - Chimica dell'Ambiente e dei Beni Culturali
Settore CHIM/02 - Chimica Fisica
correlated molecular calculations; integrated band intensities; near-infrared spectroscopy; anharmonic-force field; Gaussian-basis sets; Rovibrational analysis; centrifugal-distortion; laser spectrum; vinyl fluoride; gas-phase
Fondi MUR
grant number 2017A4XRCA
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/124282
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