A full three-dimensional global potential energy surface is reported for the ground state of CH 2 + by fitting accurate multireference configuration interaction energies calculated using aug-cc-pVQZ and aug-cc-pV5Zbasis sets with extrapolation of the electron correlation energy to the complete basis set limit. The A comparison shows that our potential energy surface can be applied to any type of dynamic study.
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.
A full three-dimensional global potential energy surface (PES), covering the whole configuration space, is reported first for the title system by fitting high-level ab initio energies at the multireference configuration interaction level with the aug-cc-pV6Z basis set. In this work, the many-body expansion method is invoked to fit the innate character of the CH2 +(12 A″) PES. The topographical features are examined in detail based on the new global PES and in accordance with the other calculations from the ab initio energies, which show the correct behavior at the C+(2P) + H2(X 1Σg +) and CH+(a 3Π) + H(2S) dissociation limits. Using a time-dependent wave packet method, we provide insights into the dynamics behavior for reaction of C+(2P) + H2(X 1Σg +) → CH+(a 3Π) + H(2S). The integral cross sections and reaction probabilities increase monotonically in terms of the collision energy.
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