TY - JOUR
T1 - A Phase-Space Electronic Hamiltonian for Molecules in a Static Magnetic Field II
T2 - Quantum Chemistry Calculations with Gauge Invariant Atomic Orbitals
AU - Bhati, Mansi
AU - Tao, Zhen
AU - Bian, Xuezhi
AU - Rawlinson, Jonathan
AU - Littlejohn, Robert
AU - Subotnik, Joseph E.
N1 - Publisher Copyright:
© 2025 American Chemical Society.
PY - 2025/5/22
Y1 - 2025/5/22
N2 - 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 ĤPS(X, P, G, B) 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 B-fields, including minimum energy structures with Πmin ≠ 0, indicating nonzero electronic motion in the ground-state.
AB - 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 ĤPS(X, P, G, B) 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 B-fields, including minimum energy structures with Πmin ≠ 0, indicating nonzero electronic motion in the ground-state.
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U2 - 10.1021/acs.jpca.4c07905
DO - 10.1021/acs.jpca.4c07905
M3 - Article
C2 - 40353803
AN - SCOPUS:105005063529
SN - 1089-5639
VL - 129
SP - 4573
EP - 4590
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 20
ER -