Theoretical study of the properties of the radical PS, its anion and cation

Moussaoui, Yahia; Ouamerali, Ourida; Maré, George R. De

doi:10.1016/s0166-1280(97)00160-7

Cited by 17 publications

(5 citation statements)

References 29 publications

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“…10 These authors also argue by applying an empirical correction of some 0.3 eV to their calculated EA-values, which range from 1.1 to 1.3 eV depending on the basis sets, that the electron affinity of PS should be 1.60 eV with an uncertainty of 0.1 eV. Recent RMP2 and UMP2 calculations performed by Moussaoui et al 40 yielded even smaller electron affinity values of 0.87 and 0.92 eV, respectively. In the present study we arrive at EA ¼ 1.42 eV for PS, and if we suppose a theoretical underestimation comparable to that for NS À , it seems plausible that the correct electron affinity could be rather close to 1.55 eV.…”

Section: No à and Homologuesmentioning

confidence: 96%

Trends in ground and excited state electron affinities of group 14, 15, and 16 mixed diatomic anions: a computational study

Kalcher

2002

Phys. Chem. Chem. Phys.

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Section: No à and Homologuesmentioning

confidence: 96%

Trends in ground and excited state electron affinities of group 14, 15, and 16 mixed diatomic anions: a computational study

Kalcher

2002

Phys. Chem. Chem. Phys.

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“…The SX molecules, X = first- or second-row atom, constitute a very attractive set of molecules for experimental and theoretical chemists because of the importance that they have in modern chemistry. − Among the various areas in which the SX are important, combustion chemistry, the semiconductor industry, and astrochemistry can be highlighted. For example, the SF radical and SSi are important in the semiconductor industry, , SO, SC, and S 2 are key intermediates in combustion chemistry 3,25-27 and atmospheric chemistry, and very recently, SB has been used in new propellants .…”

Section: Introductionmentioning

confidence: 99%

“…SN is also important in combustion chemistry as well as in solid-state chemistry since the (SN) x polymers have metallic conductivity properties . In the past decades, several experimental and theoretical studies have been performed to characterize the SX. − However, the difficulties in studying these species experimentally and the lack of an adequate treatment of the dynamical correlation in the ab initio calculations ,,,,,,− have made that characterization incomplete. Regarding thermochemistry, only the Δ f H ° 298 of SO and SC have been determined properly.…”

Section: Introductionmentioning

confidence: 99%

Systematic Coupled Cluster, Brueckner Coupled Cluster, G3, CBS-QB3, and DFT Investigation of SX Diatomics; X = First- or Second-Row Atom

Denis

2004

J. Phys. Chem. A

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The SX diatomics, X = first- or second-row atom, have been studied employing coupled cluster theory and the aug-cc-pV(X+d)Z basis sets. To estimate Δ f H°298, we have included a correction for core−valence (CV) correlation, spin−orbit splitting, and scalar-relativistic (SR) effects. For SO and SC, the estimated Δ f H°298 values are 0.5 kcal/mol within the experiment. However, for the remaining molecules, a revision of their ΔH° f ,298 are required. Deviations as large as 10 kcal/mol have been found between our best estimates and the values adopted by the NIST-JANAF tables. The proposed Δ f H°298 (±0.5kcal/mol) are 67.6 (SB), 66.7 (SN), 0.8 (SF), 47.4 (SAl), 27.9 (SSi), 38.1 (SP), 29.4 (S2), and 27.1 (SCl) kcal/mol. For comparative purposes we performed BD(T), G3, CBS-QB3, B3LYP, and B3PW91 calculations. The mean absolute error (MAE) of the G3 and CBS-QB3 Δ f H°298 with respect to our best results is 1.0 kcal/mol for both methodologies, whereas for B3LYP/6-311+G(3df) and B3PW91/6-311+G(3df), the MAE is 1.6 and 2.0 kcal/mol, respectively. At the coupled cluster level of theory, with respect to the experiment, the MAE of the equilibrium bond lengths is 0.0013 and 0.0012 Å for the first- and second-row SX, respectively. This result involves extrapolation to the CBS limit, a correction for CV and SR effects, and also a correction for complete triple excitations. Two molecules presented an unstable HF wave function, SN and SP. In both cases, the use of the CCSDT and BD(T) methods outperformed CCSD(T). Our spin−orbit corrected coupled cluster adiabatic electron affinities (EAad) are ±0.7 kcal/mol within the experiment for SN, SO, SF, and S2. However, some discrepancies were found for SC and SAl. Our best estimates are EAad(SC) = 2.3 kcal/mol and EAad(SAl) = 62.5 kcal/mol, 2.4 and 1.6 kcal/mol larger than the experimental EAad, respectively. For SB, SSi, SP, and SCl, we propose new EAad of 53.7, 12.4, 36.5, and 59.0 kcal/mol, respectively. The MAE of the CBS-QB3 and G3 EAad with respect to our estimated EAad is 0.9 kcal/mol for both methodologies, whereas for B3LYP/6-311+G(3df) and B3PW91/6-311+G(3df), the MAE are 1.9 and 2.7 kcal/mol, respectively, but 50% of the error is provided only by SC and SN.

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“…They also published the molecular parameters for the bound states and dipole moments for the X 2 , 1 4 , and 1 4 − states of PS. Later on, Moussaoui et al [54] reported the ground-state potential energy curve, dissociation energy, bond distance, and the fundamental harmonic vibrational frequency for the X 2 state of PS employing several ab initio methods. Yaghlane et al [55] studied the potential energy curves of several states that converge to the P( 4 S) + S( 3 P), P( 4 S) + S( 1 D), and P( 2 D) + S( 3 P) asymptotes using complete active space self-consistent field (CASSCF) method, followed by the multireference configuration interaction (MRCI) calculations.…”

Section: Resultsmentioning

confidence: 99%

Formation of PS through radiative association

2020

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Quantum chemical calculations within the multireference configuration interaction with single and double excitation level of theory are presented and used to obtain the rate coefficient for the radiative association of phosphorus and sulfur atoms to form phosphorus monosulfide (PS). The contribution of the 1 2 + state to spontaneous radiative association of the P( 4 S) and S( 3 P) atoms is more significant for forming PS. The computed rate constant can be represented over the 300-450 K temperature range by the form k(T) = 2.07 × 10 −22 (T∕300) 6.21 exp(−371∕T) cm 3 s −1 and over the 450-14,000 K temperature range by the relation k(T) = 3.68 × 10 −18 (T∕300) 0.337 exp(−3603∕T) cm 3 s −1 , where T is in K.

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Theoretical study of the properties of the radical PS, its anion and cation

Cited by 17 publications

References 29 publications

Trends in ground and excited state electron affinities of group 14, 15, and 16 mixed diatomic anions: a computational study

Trends in ground and excited state electron affinities of group 14, 15, and 16 mixed diatomic anions: a computational study

Systematic Coupled Cluster, Brueckner Coupled Cluster, G3, CBS-QB3, and DFT Investigation of SX Diatomics; X = First- or Second-Row Atom

Formation of PS through radiative association

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