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Globally accurate potential energy surface for PH2+ (11 A′) by using the switching function formalism

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Version 3 2021-03-22, 14:42
Version 2 2020-08-24, 11:15
Version 1 2019-11-14, 06:25
journal contribution
posted on 2021-03-22, 14:42 authored by Y. L. Lü, S. J. Chai, H. Y. Ma, S. B. Gao, Y. Q. Li

As an intermediate product of phosphorus compounds in astrophysical chemistry, PH2+(11A) has great significance in research on the PHn+ (n=04) systems. However, as a basis for studying its reaction mechanisms, PH2+(11A) lacks an accurate global potential energy surface (PES) and related dynamic reports. In this investigation, based on a multi-reference configuration interaction approach with Davidson correction, an accurate global many-body expansion PES for PH2+ in its ground state was reported by fitting extensive ab initio energies, as calculated with the correlation-consistent basis set aug-cc-pVQZ. Meanwhile, the switching function formalism was adopted to explain and distinguish the transformation between P+(1D) and P+(3P) in one-body energy terms, which ensured the correct dissociation channel in the reaction process of P+(1D)+H2({X}1Σg+)PH+(X2Π)+H(2S). The topographical characteristics of the title system PES were meticulously contrasted with those in other literature reports, which were consistent with previous experimental and theoretical values. Subsequently, the time-dependent wave packet approach was adopted to calculate the reaction probability and integral cross-section for the reaction P+(1D)+H2({X}1Σg+)(v=0,j=0)PH+(X2Π)+H(2S) to verify the accuracy of the new PES. This dynamics study may help to further explain the thermochemical reactions of phosphorus-containing molecules in interstellar media.

Funding

This work was supported by the National Natural Science Foundation of China [grant number 11874241], the High-level Innovative Talents Program of Shenyang City [grant number RC180230], and the Shandong Province Higher Educational Science and Technology Program [grant numbers J15LJ03 and J17KA186].; Natural Science Foundation of Liaoning Province

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