2024/11/21 by Mansi Bhati, Bhati, Mansi, Zhen Tao +9 · 1 citation
Chemistry · Materials Science · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced Physical and Chemical Molecular Interactions #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Magnetism in coordination complexes
paper · pdf · doi:10.48550/arxiv.2411.13879
openalex publication_date 2024/11/21 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
In a companion paper, we have developed a phase-space electronic structure theory of molecules in magnetic fields, whereby the electronic energy levels arise from diagonalizing a phase-space Hamiltonian HPS(\bfX,\bfΠ) that depends parametrically on nuclear position and momentum. The resulting eigenvalues are translationally invariant; moreover, if the magnetic field is in the z-direction, then the eigenvalues are also invariant to rotations around the z-direction. However, like all Hamiltonians in a magnetic field, the theory has a gauge degree of freedom (corresponding to the position of the magnetic origin in the vector potential), and requires either (i) formally, a complete set of electronic states or (ii) in practice, gauge invariant atomic orbitals (GIAOs) in order to realize such translational and rotational invariance. Here we describe how to implement a phase-space electronic Hamiltonian using GIAOs within a practical electronic structure package (in our case, Q-Chem). We further show that novel phenomena can be observed with finite \bfB-fields, including minimum energy structures with \bfΠmin ≠ 0, indicating non-zero electronic motion in the ground-state.