Fluoro Hydrogen Peroxide: A Plausible Molecular Form of Naturally-Occurring Fluorine

Abstract

Fluorine's hostile nucleosynthetic environment makes it one of the least common elements and, consequently, understudied both on the earth and in the interstellar medium (ISM). However, the presence of fluorine-containing species in both the ISM and in the earth's atmosphere necessitates the existence of a pathway out of this environment to form fluorinecontaining molecules. To that end, the presence of fluorine and hydroperoxyl radical (HO 2 ) in either of these environments may lead to the formation of fluorinated molecules like fluoro hydrogen peroxide (HOOF) on dust grains of protoplanetary disks in the planet-forming regions of ρ Oph and in the earth's atmosphere as a sink for other fluorine pollutants that have yet to be detected. This theoretical study utilizes explicitly correlated coupled cluster theory computed with core correlation and corrections from scalar relativity to provide the first anharmonic fundamental vibrational frequencies and rotational constants of HOOF for use as reference benchmarking of further computational or experimental study, as well as potential astrophysical observation. The ν 6 bending frequency for HOOF at 454.4 cm −1 exhibits an anharmonic transition intensity of 78 km/mol, while the ν 4 frequency at 738.2 cm −1 is 66 km/mol. Additionally, HOOF has a large net dipole moment of 2.12 D compared to the previously detected HF and HOOH molecules, 1.82 and 1.85 D, respectively, resulting from the electronegativity of the fluorine. Consequently, HOOF is a likely candidate for possible detection via vibrational and rotational spectroscopy to further the understanding of fluorine's small, but important, role in astrochemical and atmospheric environments.

Reaction Pathway and Rovibrational Analysis of Aluminum Nitride Species as Potential Dust Grain Nucleation Agents

“…QFFs as employed herein have been able to produce rovibrational spectroscopic constants within 1% of experimental values for many molecular systems (Huang & Lee 2008Huang et al 2011Huang et al , 2013Fortenberry et al 2014;Zhao et al 2014;Fortenberry et al 2015;Kitchens & Fortenberry 2016;Fortenberry 2017;Fortenberry et al 2018;Gardner et al 2021). F12-TZ has been shown to produce accurate fundamental vibrational frequencies and rotational constants at far less computational cost compared to other QFF methods (Martin & Kesharwani 2014;Inostroza-Pino et al 2020;Palmer & Fortenberry 2022). Additionally, the QFF implemented in this work is conducted within the recently developed automated PBQFF framework (Westbrook & Fortenberry 2023).…”

Spectroscopy and Photochemistry of OAlNO and Implications for New Metal Chemistry in the Atmosphere

“…This QFF method utilized herein uses the CCSD­(T)-F12b level with the inclusion of explicit core–electron correlation in the cc-pCVTZ-F12 basis set and scalar relativistic corrections also present in the previous composite methodology. This new composite method will henceforth be abbreviated “F12-TZ-cCR.” The F12-TZ-cCR methodology has been previously used to produce more accurate rovibrational spectroscopic data than that of both F12-TZ and other canonical CCSD­(T)-based composite methods with the added benefit of a decrease in computational cost compared to the composite method. − Consequently, the F12-TZ-cCR QFF is employed herein to provide accurate predictions for the rovibrational character of the aluminum-containing species investigated in this work.…”