Electronic quantum motions in hydrogen molecule ion

The hydrogen molecule ion is a two‐center force system expressed under the prolate spheroidal coordinates, whose quantum motions and quantum trajectories have never been addressed in the literature before. The momentum operators in this coordinate system are derived for the first time from the Hamilton equations of motion and used to construct the Hamiltonian operator. The resulting Hamiltonian comprises a kinetic energy T and a total potential V_Total consisting of the Coulomb potential and a quantum potential. It is shown that the participation of the quantum potential and the accompanied quantum forces in the force interaction within H₂⁺ is essential to develop an electronic motion consistent with the prediction of the probability density function |Ψ|². The motion of the electron in H₂⁺ can be either described by the Hamilton equations derived from the Hamiltonian H = T_K + V_Total or by the Lagrange equations derived from the Lagrangian H = T_K ? V_Total. Solving the equations of motion with different initial positions, we show that the solutions yield an assembly of electronic quantum trajectories whose distribution and concentration reconstruct the σ and π molecular orbitals in H₂⁺. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011