Ab initio study on the low-lying excited states of gas-phase PH+ cation including spin–orbit coupling
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Cited by 6 publications
References 20 publications
The global potential energy surface of PH2+(21A′) extrapolated to the complete basis set limit
It has been established that the proton transfer dynamics of P + ( P 3 ) + H 2 ( X 1 Σ g + ) → P H + ( A 2 Δ ) + H ( S 2 ) play an important role in determining the chain reaction of phosphorus-containing P H n + ( n = 0 − 4 ) compounds in the planetary ionosphere. This work presents an accurate global potential energy surface (PES) of P H 2 + ( 2 1 A ′ ) for the first time by fitting extensive ab initio energies from the aug-cc-pV(T, Q)Z level of theory using the multi-reference configuration interaction method including Davidson correction, and extrapolating the points to the complete basis set limit. The spectral parameters of PH+(A 2Δ) and H 2 ( X 1 Σ g + ) are shown to be in agreement with the data available in previous literature. Meanwhile, a detailed study of the topographical features of the global PES could be used as a reliable photolytic kinetic theory for the P + ( P 3 ) + H 2 ( X 1 Σ g + ) reaction. Furthermore, to demonstrate the validity of the new PES, we have explicitly taken into account the P + ( P 3 ) + H 2 ( X 1 Σ g + ) ( v = 0 , j = 0 ) → P H + ( A 2 Δ ) + H ( S 2 ) reaction, and assessed its feasibility in terms of reaction dynamics by calculating the integral cross-section via the time-dependent wave packet and quasi-classical trajectory approaches. The consequent results indicate that the new PES is suitable for thermochemical reactions.
The global potential energy surface of PH2+(21A′) extrapolated to the complete basis set limit
It has been established that the proton transfer dynamics of P + ( P 3 ) + H 2 ( X 1 Σ g + ) → P H + ( A 2 Δ ) + H ( S 2 ) play an important role in determining the chain reaction of phosphorus-containing P H n + ( n = 0 − 4 ) compounds in the planetary ionosphere. This work presents an accurate global potential energy surface (PES) of P H 2 + ( 2 1 A ′ ) for the first time by fitting extensive ab initio energies from the aug-cc-pV(T, Q)Z level of theory using the multi-reference configuration interaction method including Davidson correction, and extrapolating the points to the complete basis set limit. The spectral parameters of PH+(A 2Δ) and H 2 ( X 1 Σ g + ) are shown to be in agreement with the data available in previous literature. Meanwhile, a detailed study of the topographical features of the global PES could be used as a reliable photolytic kinetic theory for the P + ( P 3 ) + H 2 ( X 1 Σ g + ) reaction. Furthermore, to demonstrate the validity of the new PES, we have explicitly taken into account the P + ( P 3 ) + H 2 ( X 1 Σ g + ) ( v = 0 , j = 0 ) → P H + ( A 2 Δ ) + H ( S 2 ) reaction, and assessed its feasibility in terms of reaction dynamics by calculating the integral cross-section via the time-dependent wave packet and quasi-classical trajectory approaches. The consequent results indicate that the new PES is suitable for thermochemical reactions.
The radiative association of PO/PH+ and the photodissociation of PH+
The potential energy curves (PECs) and transition dipole moments (TDMs) of PH+ and PO are computed with the multireference configuration interaction method, and the cross-sections for the radiative association (RA) of PH+ and PO, which is the most efficient way to form the ground states, are presented via the quantum mechanical (QM) theory and computed using ab initio molecular data. The thermal rate coefficients are also expressed and fitted with the standard formula kT=AT300αe−βT in the range of 10 K–15,000 K. Meanwhile, the photodissociation, that is the inverse process of RA for PH+, is also studied, including eight photodissociation channels for the computation of state-resolved cross-sections. Careful comparisons with the Leiden Observatory database are made. Considering the cross-sections mentioned above, the local thermodynamic equilibrium cross-sections at the temperatures of 0, 500, 1,000, and 2,000 K are also shown. We expect the results to be helpful for studies of phosphorus chemistry in the interstellar medium and planetary atmospheres.
Global Analytic Potential Energy Surface of PH2 + (13A ″) and Dynamics Studies of the P+(3P ) + D2 Reaction
The global potential energy surface (PES) of PH2+(13A″) was constructed using permutation invariant polynomial neural network method based on 18 566 ab initio energy points. In ab initio calculation, aug‐cc‐pVQZ and aug‐cc‐pwCVQZ basis sets were used for H and P+, respectively. The topographic features of the PES were discussed in detail and compared with available theoretical and experimental values. The results indicate that the PES is well fitted by using neural network method. In addition, quasi‐classical trajectory (QCT) calculations were carried out for the P+(3P) + D2 reaction in the collision energy range from 1.2 to 8.0 eV. The integral cross sections were reported and compared with experimental data. The differential cross sections were also calculated, and it reflects that the “complex‐forming” mechanism dominates the reaction in the low collision energy range, and direct abstraction mechanism plays a dominant role in the high collision energy range.
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