A Phase-Space Electronic Hamiltonian for Molecules in a Static Magnetic Field II: Quantum Chemistry Calculations with Gauge Invariant Atomic Orbitals
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| Main Authors: | , , , , , |
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| Format: | Preprint |
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2024
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| _version_ | 1866929600176586752 |
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| author | Bhati, Mansi Tao, Zhen Bian, Xuezhi Rawlinson, Jonathan Littlejohn, Robert Subotnik, Joseph E. |
| author_facet | Bhati, Mansi Tao, Zhen Bian, Xuezhi Rawlinson, Jonathan Littlejohn, Robert Subotnik, Joseph E. |
| contents | 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 $\hat H_{PS}(\bf{X},\bfΠ)$ 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 $\bf{B}-$fields, including minimum energy structures with $\bfΠ_{min} \ne 0$, indicating non-zero electronic motion in the ground-state. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2411_13879 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | A Phase-Space Electronic Hamiltonian for Molecules in a Static Magnetic Field II: Quantum Chemistry Calculations with Gauge Invariant Atomic Orbitals Bhati, Mansi Tao, Zhen Bian, Xuezhi Rawlinson, Jonathan Littlejohn, Robert Subotnik, Joseph E. Chemical Physics 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 $\hat H_{PS}(\bf{X},\bfΠ)$ 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 $\bf{B}-$fields, including minimum energy structures with $\bfΠ_{min} \ne 0$, indicating non-zero electronic motion in the ground-state. |
| title | A Phase-Space Electronic Hamiltonian for Molecules in a Static Magnetic Field II: Quantum Chemistry Calculations with Gauge Invariant Atomic Orbitals |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2411.13879 |