Ab initio calculation of rovibrational states for non-degenerate double-well potentials: cis–trans isomerization of HOPO

Erfort, Sebastian; Tschöpe, Martin; Rauhut, Guntram; Zeng, Xiaoqing; Tew, David P.

doi:10.1063/5.0005497

Cited by 14 publications

(5 citation statements)

References 36 publications

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“…A similar approach has been found to be effective in fitting compact and accurate analytic potentials for malonaldehye, [38] formic acid, [39,40] and metaphosphosous acid. [41] The form of the zeroth-order model potential was chosen to be…”

Section: B Data Point Generationmentioning

confidence: 99%

Computational study of the rovibrational spectrum of H2O-HF

Viglaska

Wang

Carrington

et al. 2022

Journal of Molecular Spectroscopy

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Section: B Data Point Generationmentioning

confidence: 99%

Computational study of the rovibrational spectrum of H2O-HF

Viglaska

Wang

Carrington

et al. 2022

Journal of Molecular Spectroscopy

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“…Some of these are based on the seminal work of Watson (1968), introducing the respective Hamiltonian. Subsequently, vibrational configuration interaction (VCI) theory (Bowman et al 1979;Christoffel & Bowman 1982;Neff & Rauhut 2009;Pfeiffer & Rauhut 2014;) was introduced for nonrotating molecules and after that rovibrational configuration interaction (RVCI) theory (Erfort et al 2020a(Erfort et al , 2020b(Erfort et al , 2022 for the simulation of rotating molecules. These approaches rely on high-level potential energy surfaces (PESs) (Ziegler & Rauhut 2016, 2018 for the efficient calculation of rovibrational line lists and spectra for semirigid molecules.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Characterization of Diazophosphane—A Candidate for Astrophysical Observations

Tschöpe

Rauhut

2023

ApJ

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Quite recently, diazophosphane, HP−N≡N, was synthesized for the first time. This was accomplished by a reaction of PH3 with N2 under UV irradiation at 193 nm. As these two molecules have been observed in different astrophysical environments, as for example, in the circumstellar medium and, in particular, in the AGB star envelope IRC+10216, the question arises whether HPN2 can be found as well. So far there is only the aforementioned experimental work, but neither rotational nor rovibrational data are available. Hence, the lack of accurate line lists, etc. to identify diazophosphane is the subject of this work, including a detailed analysis of the rotational, vibrational, and rovibrational properties for this molecule. Our calculations rely on multidimensional potential energy surfaces obtained from explicitly correlated coupled-cluster theory. The (ro)vibrational calculations are based on related configuration interaction theories avoiding the need for any model Hamiltonians. The rotational spectrum is studied between T = 10 and 300 K. In contrast, the partition functions for HPN2 and DPN2 are given and compared for temperatures up to 800 K. In addition, more than 70 vibrational transitions are calculated and analyzed with respect to resonances. All these vibrational states are considered within the subsequent rovibrational calculations. This allows for a detailed investigation of the infrared spectrum up to 2700 cm−1 including rovibrational couplings and hot bands. The results of this study serve as a reference and allow, for the first time, for the identification of diazophosphane, for example, in one of the astrophysical environments mentioned above.

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“…of CPO with hydroxyl radical (COH) to yield metaphosphorus acid (HOPO) [9] involves in the oxidation of phosphines. [10] Particularly, this reaction was supposed to be responsible for the bright glow with visible chemiluminescence extending down to 360 nm during the combustion of PH 3 .…”

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confidence: 99%

“…The photolysis of cis-HOPO [9] in a solid Ar-matrix was first performed by using a 266 nm laser. The resulting IR difference spectrum (Figure 1 A) shows the depletion of cis-HOPO (a, 3555.4/3548.4, 1252.6, 904.5, 841.5, and 523.9/ 517.4 cm À1 ) [9a] and the appearance of CPO 2 (d, 1325.6 cm À1 ).…”

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confidence: 99%

The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

et al. 2020

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Phosphorus monoxide (CPO) is a key intermediate in phosphorus chemistry, and its association with the hydroxyl radical (COH) to yield metaphosphorous acid (cis-HOPO) contributes to the chemiluminescence in the combustion of phosphines. When photolyzing cis-HOPO in an Ar-matrix at 2.8 K, the simplest dioxophosphorane HPO 2 and an elusive hydroxyl radical complex (HRC) of CPO form. This prototypical radical-radical complex reforms into cis-HOPO at above 12.0 K by overcoming a barrier of 0.28 AE 0.02 kcal mol À1. The vibrational spectra of this HRC and its D-and 18 Oisotopologues suggest a structure of COH•••OPC, for which a triplet spin multiplicity with a binding energy of À3.20 kcal mol À1 has been computed at the UCCSD(T)-F12a/aug-cc-pVTZ level.

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Ab initio calculation of rovibrational states for non-degenerate double-well potentials: cis–trans isomerization of HOPO

Cited by 14 publications

References 36 publications

Computational study of the rovibrational spectrum of H2O-HF

Computational study of the rovibrational spectrum of H2O-HF

Spectroscopic Characterization of Diazophosphane—A Candidate for Astrophysical Observations

The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

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