Adiabatic Jacobi corrections for H2+-like systems

Area of Science:

• Quantum Chemistry
• Theoretical Molecular Physics
• Computational Chemistry

Background:

• The Coulomb three-body problem is fundamental in molecular physics.
• Accurate calculations require accounting for finite nuclear masses.
• Born-Oppenheimer approximations simplify calculations but have limitations.

Purpose of the Study:

• To solve the Coulomb three-body problem in Jacobi coordinates for diatomic molecular ions.
• To introduce and compute adiabatic Jacobi corrections (AJCs) for finite nuclear masses.
• To investigate the behavior of electronic energies and particle distances in H2+, D2+, and HD+.

Main Methods:

• Solving the Coulomb three-body problem using Jacobi coordinates.
• Treating the distance of equally charged particles as a parameter.
• Calculating electronic energies and adiabatic Jacobi corrections (AJCs) for finite nuclear masses.

Main Results:

• Computed rotationless ground-state electronic and AJC energies for H2+, D2+, and HD+.
• AJCs were found to be smaller than traditional Born-Oppenheimer corrections.
• Computed expectation values of internuclear distances and demonstrated symmetry breaking in HD+.

Conclusions:

• The proposed method accurately computes electronic energies with finite nuclear masses.
• AJCs provide a valuable correction beyond the standard Born-Oppenheimer approximation.
• The method successfully captures symmetry breaking phenomena in molecular ions like HD+.