The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

Chu, Xianxu; Qian, Weiyu; Lü, Bo; Wang, Lina; Qin, Jie; Li, Jun; Rauhut, Guntram; Trabelsi, Tarek; Francisco, Joseph S.; Zeng, Xiaoqing

doi:10.1002/ange.202011512

Cited by 2 publications

(1 citation statement)

References 76 publications

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“…Among the species that may exist in a CSE or serve as intermediates in chemical reactions includes [H, S, P, O]. This molecular system is isoelectronic to the well-known nitrous acid (HONO) (Ramazan et al 2004), metaphosphorous acid (HOPO) (Bell et al 2000;Chu et al 2020), and thionitrous acid or Snitrosothiol [H, S, N, O] (Filipovic et al 2012), which play important roles in atmospheric and biological medium. For example, the hydrolysis of NO 2 is a major source of HONO and subsequently OH radicals in polluted urban areas (Ramazan et al 2004).…”

Section: Introductionmentioning

confidence: 99%

Astrochemical significance and spectroscopy of tetratomic [H, P, S, O]

Esposito

Friskey

Trabelsi

et al. 2022

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Context. Phosphorus is integral to life on Earth, and its role in the chemistry of the interstellar medium is highly debated and unknown. Only a handful of phosphorus-bearing species have been detected thus far, with the most recent confirmed detection taking place in 2014. The simultaneous detection of molecules such as PO, SH, and OH indicate the possibility of reactive intermediate species existing in the interstellar medium and circumstellar envelopes of evolved stars. To explore this possibility, the [H, P, S, O] tetratomic isomer family was characterized using high level ab intio methods. Aims. The aim of this study is to provide rotational, vibrational, and electronic spectroscopic data to drive experimental and observational detection of new phosphorus and sulfur-bearing molecules. Additionally, chemical pathways are explored to explain possible reservoirs for the as of yet undetected PH and PS diatomic molecules. Methods. Coupled cluster quantum chemistry methods were used to calculate the equilibrium electronic structure followed by the anharmonic treatment of the cubic and quartic force fields to obtain accurate rotational and vibrational data. Møller-Plesset perturbation theory in conjunction with coupled cluster methods were used to explore bimolecular reaction pathways. Multi-reference methods were then used to characterize the photochemical pathways of the excited electronic states and simulate the electronic absorption spectrum.Results. The reaction between detected molecules SH and PO is highly exothermic and forms the HSPO isomer. Deeply submerged transition state barriers allow for facile isomerization to other isomers, especially HOPS. The dominant photochemical process predicted for HOPS is dissociation to form OH + PS, while that of HSPO is a combination of photodissociation to form H + SPO and SH + PO, depending on the wavelength of light absorbed. If PH and PS are formed in the early outflows from evolved stars, bimolecular reactions may act as a reservoir and partially account for their lack of detection to date. The electronic absorption spectrum is predicted to be congested in the 175 -200 nm region for both HOPS and HSPO. Differentiating peaks exist > 400 nm, which can be used for spectral assignment. Vibrationally corrected rotational constants and anharmonic vibrational frequencies were calculated to assist in the laboratory and observation identification of the most stable molecules. The PO stretch is predicted to be the most intense vibrational mode in both HOPS isomers, and a frequency difference of 20 cm −1 may prove to help differentiate the conformers in an experimental spectrum.

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Section: Introductionmentioning

confidence: 99%

Astrochemical significance and spectroscopy of tetratomic [H, P, S, O]

Esposito

Friskey

Trabelsi

et al. 2022

A&A

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Spectroscopic Identification and Photochemistry of Astrochemically Relevant Phosphorus-bearing Molecules [O, C, N, P] and [2O, C, N, P]

Zhu,

Wang,

Jiang

et al. 2024

ApJ

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Diatomic molecules phosphorus monoxide (PO) and phosphorus mononitride (PN) are the main reservoirs of gas-phase phosphorus in interstellar and circumstellar environments, indicating the possibility of forming new phosphorus-bearing molecules through reactions with other interstellar species. To explore the astrochemistry of PO and PN, new simple phosphorus-bearing molecules [O, C, N, P] and [2O, C, N, P] were generated in the gas phase and isolated in cryogenic matrices for characterization with matrix-isolation IR and UV/vis spectroscopy in combination with calculations at the CCSD(T)-F12a/VTZ-F12 level of theory. In an inert argon matrix, OPCN isomerizes to OPNC upon UV-light irradiation at 365 nm, followed by successive isomerizations to PNCO and POCN with concomitant dissociation to diatomic PN and CO under further irradiation at 193 nm. By analogy, the isomerization of O2PCN to O2PNC and OPNCO followed by fragmentation to OPN/CO and PN/CO2 occurs in the matrix upon irradiation at 193 nm. In a chemically active CO ice, the photolytic reaction of OPCN with CO yields CO2 and PCN, and O2PCN reacts with CO by forming OPCN and CO2, in which the photochemical networks for these P-bearing species linking the astrochemically important PN and PO have been proposed. The experimental identification of these phosphorus-bearing molecules is supported by quantum chemical calculations, and the spectroscopic data may aid in their detection in the interstellar and circumstellar medium.

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The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

Cited by 2 publications

References 76 publications

Astrochemical significance and spectroscopy of tetratomic [H, P, S, O]

Astrochemical significance and spectroscopy of tetratomic [H, P, S, O]

Spectroscopic Identification and Photochemistry of Astrochemically Relevant Phosphorus-bearing Molecules [O, C, N, P] and [2O, C, N, P]

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