Potential Energy Curves of the Low-Lying Five 1Σ+ and 1Π States of a CH+ Molecule Based on the Free Complement - Local Schrödinger Equation Theory and the Chemical Formula Theory.

Abstract

The potential energy curves (PECs) of the low-lying five 1Σ+ and 1Π states (X1Σ+, C1Σ+, 31Σ+, A1Π, and D1Π states) of a CH+ molecule, an important interstellar molecule, were calculated by the free complement (FC) - local Schrödinger equation (LSE) theory with the direct local sampling scheme. The FC wave functions were constructed based on the chemical formula theory (CFT), whose local characters correspond to the covalent dissociations: C+(2P°(s2p))) + H(2S) of the X1Σ+ and A1Π states and the ionic dissociations: C(1D(s2p2)) + H+ of the C1Σ+ and D1Π states. All the calculated PECs were obtained with satisfying the chemical accuracy, i.e., error less than 1 kcal/mol, as absolute total energy of the Schrödinger equation without any energy shift. The spectroscopic data calculated from the PECs agreed well with both experimental and other accurate theoretical references. We also analyzed the wave functions using the inverse overlap weights proposed by Gallup et al. with the CFT configurations. For the X1Σ+ and A1Π states, the covalent C+(sp2) and C+(p3) configurations played important roles for bond formation. In the small internuclear distances of the C1Σ+, D1Π, and 31Σ+ states, the covalent character was also dominant as a result of the electron charge transfer from C to H+. Thus, the present FC-LSE results not only are accurate but also can provide chemical understanding according to the CFT.