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

An accurate NH2(X2A′′) CHIPR potential energy surface via extrapolation to the complete basis set limit and dynamics of the N(2D) + H2(X1Σ+g) reaction

“…With potential energies extrapolated to the CBS limit, the V N( 2 D) equals to 0.08765 E h , which agrees well with the experimental value 42 of 0.08759 E h . The f ( R ) is assumed as the following form 26,41,43 f ( R ) = h ( R 1 ) g ( r 1 ) g ( r 1 ) = 0.5{1 + tanh[ α 0 ( r 1 − r 0 1 )]}where R 1 is the H–H bond length, r 1 is the length from the N atom to the center of the mass for H–H. In the N( 2 D) + H 2 (X 1 Σ + g ) channel, the function h ( R 1 ) ensures the decay from the N( 2 D) state to the N( 4 S) state as the H–H bond length increases.…”

“…Hence, it is necessary to introduce a function to switch the excited state N( 2 D) to the ground state N( 4 S) in the N( 2 D) + H 2 (X 1 Σ + g ) → H( 2 S) + NH(X 3 Σ − ) dissociation process. Here, we adopt a procedure used by Lü et al , 41 which successfully fulfilled the transformation between P + ( 1 D) and P + ( 3 P) while constructing the global PES of PH 2 + (1 1 A′).…”

The global potential energy surface of PH2+(21A′) extrapolated to the complete basis set limit

“…To further verify the accuracy of the proposed PES, we calculate the molecular reaction dynamics of the new PES using dif-ferent dynamic calculation methods, namely the QCT method [57] and the quantum TDWP method [45][46][47][48][49].…”