The global potential energy surface of extrapolated to the complete basis set limit,Journal of Physics B: Atomic, Molecular and Optical Physics

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The global potential energy surface of extrapolated to the complete basis set limit
Journal of Physics B: Atomic, Molecular and Optical Physics ( IF 1.6 ) Pub Date : 2021-04-22 , DOI: 10.1088/1361-6455/abece4
Yanling L ₁ , Chengyuan Zhang ₁ , Hongyu Ma ₁ , Qiang Guo ₂ , Yongqing Li _{1,

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Affiliation

It has been established that the proton transfer dynamics of ${\text{P}}^{+}\left({}^{3}P\right)+{\text{H}}_{2}\left({X}^{1}{{\Sigma}}_{\mathrm{g}}^{+}\right)\to \text{P}{\text{H}}^{+}\left({A}^{2}{\Delta}\right)+\text{H}\left({}^{2}S\right)$ play an important role in determining the chain reaction of phosphorus-containing ${\mathrm{P}\mathrm{H}}_{n}^{+}\left(n=0-4\right)$ compounds in the planetary ionosphere. This work presents an accurate global potential energy surface (PES) of ${\mathrm{P}\mathrm{H}}_{\mathrm{2}}^{+}\left({\mathrm{2}}^{\mathrm{1}}{A}^{\prime }\right)$ 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 ${\mathrm{H}}_{\mathrm{2}}\left({X}^{\mathrm{1}}{{\Sigma}}_{\mathrm{g}}^{+}\right)$ 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 ${\mathrm{P}}^{+}\left({}^{3}P\right)+{\mathrm{H}}_{\mathrm{2}}\left({X}^{\mathrm{1}}{{\Sigma}}_{\mathrm{g}}^{+}\right)$ reaction. Furthermore, to demonstrate the validity of the new PES, we have explicitly taken into account the ${\text{P}}^{+}\left({}^{3}P\right)+{\text{H}}_{2}\left({X}^{1}{{\Sigma}}_{\mathrm{g}}^{+}\right)\left(v=0,j=0\right)\to \text{P}{\text{H}}^{+}\left({A}^{2}{\Delta}\right)+\text{H}\left({}^{2}S\right)$ 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.

中文翻译：

外推到完全基组极限的全局势能面

已经确定，质子转移动力学 ${\text{P}}^{+}\left({}^{3}P\right)+{\text{H}}_{2}\left({X}^{1}{{\ Sigma}}_{\mathrm{g}}^{+}\right)\to \text{P}{\text{H}}^{+}\left({A}^{2}{\Delta} \right)+\text{H}\left({}^{2}S\right)$ 在确定 ${\mathrm{P}\mathrm{H}}_{n}^{+}\left(n=0-4\right)$ 行星电离层中含磷化合物的链式反应中起着重要作用。这项工作 ${\mathrm{P}\mathrm{H}}_{\mathrm{2}}^{+}\left({\mathrm{2}}^{\mathrm{1}}{A}^{\prime }\对)$ 通过使用包括戴维森校正在内的多参考构型相互作用方法拟合来自 aug-cc-pV(T, Q)Z 理论水平的广泛从头算能量，首次提出了准确的全局势能面 (PES) ，并将这些点外推到完整的基组极限。PH ⁺ ( A ² Δ) 和 ${\mathrm{H}}_{\mathrm{2}}\left({X}^{\mathrm{1}}{{\Sigma}}_{\mathrm{g}}^{+}\right )$ 显示与先前文献中可用的数据一致。同时，对全球 PES 地形特征的详细研究可用作该 ${\mathrm{P}}^{+}\left({}^{3}P\right)+{\mathrm{H}}_{\mathrm{2}}\left({X}^{\ mathrm{1}}{{\Sigma}}_{\mathrm{g}}^{+}\right)$ 反应的可靠光解动力学理论。此外，为了证明新 PES 的有效性，我们明确考虑了 ${\text{P}}^{+}\left({}^{3}P\right)+{\text{H}}_{2}\left({X}^{1}{{\ Sigma}}_{\mathrm{g}}^{+}\right)\left(v=0,j=0\right)\to \text{P}{\text{H}}^{+}\ left({A}^{2}{\Delta}\right)+\text{H}\left({}^{2}S\right)$ 反应，并通过时间相关波包和准经典轨迹方法计算积分截面来评估其在反应动力学方面的可行性。结果表明，新的 PES 适用于热化学反应。

更新日期：2021-04-22

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