Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

arXiv:2410.19963 · Physical Review Letters

Hyperfine Rovibrational States of H 3 + in a Weak External Magnetic Field

Gustavo Avila, Ayaki Sunaga, Stanislav Komorovský, Edit Mátyus

Published Jun 3, 2025• 1 citation
arXivHTMLPDF

Abstract

Rovibrational energies, wave functions, and Raman transition moments are reported for the lowest-energy states of the H_{3}^{+} molecular ion including the magnetic couplings of the proton spins and molecular rotation in the presence of a weak external magnetic field. The rovibrational-hyperfine-Zeeman Hamiltonian matrix is constructed and diagonalized using the rovibrational eigenstates and the proton spin functions. The developed methodology can be used to compute hyperfine-Zeeman effects also for higher-energy rovibrational excitations of H_{3}^{+} and other closed-shell polyatomic molecules. These developments will guide future experiments extending quantum logic spectroscopy to polyatomic systems.

DOI
10.1103/lclp-852d

Related papers

A Quantum Mechanical Approach to the Computation of Rovibrational Spectra of Diatomic Molecules in Strong Magnetic Fields

Nikhil Yenugu, Ashwani K Tiwari, Sangita Sen

In the absence of experimental data for molecular spectra in strong magnetic fields, high resolution and reliable computational spectra are required for the interpretation of spectra collected from highly magnetic astrophysical objects. In this paper, we extend the Wilson-Hamiltonian framework, recently implemented and benchmarked by us (\textit{J. Chem. Theory Comput.}, \textbf{21}, 9753 (2025) ), to a general three-dimensional framework suitable for computing the rovibrational spectra of diatomic molecules in strong uniform magnetic fields. The field-dependent electronic and nuclear Hamiltonians capture full non-perturbative coupling between particle motion and the field making the method applicable to all field strengths. The electric quadrupole transition moment integrals for rovibrational transitions in external static magnetic fields are formulated, implemented, and computed to yield spectra which respect the selection rules of the molecule-field system. The spectral changes with increasing field strength such as shifting, splitting, merging, appearance and disappearance of peaks are noted. Contributions from electrons and nuclei are studied individually, as well as in unison to reveal the underlying physics such as stiffening of the bond, emergence of a rotational barrier, field-induced coupling/decoupling of states, and symmetry-breaking in rotational and vibrational states. These results provide the first fully quantum mechanical computational results for the rovibrational signature of $^1\mathrm{H}_{2}$ in extreme magnetic field environments with accuracy suitable for experimental interpretation. The methodology developed herein has direct relevance for high-field spectroscopy and astrochemical modeling, both for providing computational data as well as for understanding the spectral impact of strong magnetic fields on electronic structure and nuclear motion in molecules.

physics.chem-phCross-listedarXiv:2607.27907•Jul 31, 2026

Cold collisions of polyatomic molecular radicals with S-state atoms in a magnetic field: An ab initio study of He + ${\rm CH}_2(\tilde{X})$ CH 2(X) collisions

Timur V. Tscherbul, Timur A. Grinev, Hua‐Gen Yu +4 more

We develop a rigorous quantum mechanical theory for collisions of polyatomic molecular radicals with S-state atoms in the presence of an external magnetic field. The theory is based on a fully uncoupled space-fixed basis set representation of the multichannel scattering wave function. Explicit expressions are presented for the matrix elements of the scattering Hamiltonian for spin-1/2 and spin-1 polyatomic molecular radicals interacting with structureless targets. The theory is applied to calculate the cross sections and thermal rate constants for spin relaxation in low-temperature collisions of the prototypical organic molecule methylene [CH(2)(X(3)B(1))] with He atoms. To this end, two accurate three-dimensional potential energy surfaces (PESs) of the He-CH(2)(X(3)B(1)) complex are developed using the state-of-the-art coupled-cluster method including single and double excitations along with a perturbative correction for triple excitations and large basis sets. Both PESs exhibit shallow minima and are weakly anisotropic. Our calculations show that spin relaxation in collisions of CH(2), CHD, and CD(2) molecules with He atoms occurs at a much slower rate than elastic scattering over a large range of temperatures (1 μK-1 K) and magnetic fields (0.01-1 T), suggesting excellent prospects for cryogenic helium buffer-gas cooling of ground-state ortho-CH(2)(X(3)B(1)) molecules in a magnetic trap. Furthermore, we find that ortho-CH(2) undergoes collision-induced spin relaxation much more slowly than para-CH(2), which indicates that magnetic trapping can be used to separate nuclear spin isomers of open-shell polyatomic molecules.

arXiv:1209.3071•The Journal of Chemical Physics•Sep 10, 2012•10 citations

Rovibrational structure and electric dipole moments of the AcOCH$_3$+ ion

Anna Zakharova

The possibility of laser cooling and the presence of closely spaced rovibrational doublets make polyatomic molecules an attractive platform for the $\mathcal{P}$, $\mathcal{T}$-violation searches. We study the spectrum of the lowest rovibrational state of the AcOCH$_3+$ symmetric top molecule. The electronic structure full-electron computation was performed within a relativistic coupled cluster method with double and perturbative triple excitations. The rovibrational wavefunctions are obtained using a coupled channel technique, taking into account all rovibrational effects and anharmonicities of the potential. As a result, the vibrational frequencies, as well as the values of the electric dipole moments for the rovibrational states, were computed.

physics.atom-phCross-listedarXiv:2605.15121•May 15, 2026

Nondestructive Control of the Rovibrational Ground State of a Single Molecular Hydrogen Ion in a Penning Trap

C. M. König, F. Heiße, Jonathan Morgner +6 more

In this work, we demonstrate a new method for quantum state control and nondestructive internal quantum state readout of a single HD^{+} ion in the rovibrational ground state in a Penning trap. Furthermore, we demonstrate a measurement of the magnetic trapping field with the same ion to sub-ppb uncertainty. This could enable nondestructive, high-precision spectroscopy of the hyperfine, Zeeman, and rovibrational level structure of single molecular ions. In particular, this technique can be applied to H_{2}^{+} as well as to its antimatter equivalent, H[over ¯]_{2}^{-}, with the potential for high-precision tests of charge-parity-time reversal symmetry beyond current sensitivities [Phys. Scr. T 1995, 423 (1995)PHSTBO0031-894910.1088/0031-8949/1995/T59/060, Phys. Rev. A 98, 010101 (2018)PLRAAN2469-992610.1103/PhysRevA.98.010101].

Physical Review Letters•Apr 24, 2025•7 citations

Hyperfine and Zeeman interactions in ultracold collisions of molecular hydrogen with atomic lithium

Hubert Jóźwiak, Timur V. Tscherbul, Piotr Wcisło

We present a rigorous quantum scattering study of the effects of hyperfine and Zeeman interactions on cold Li-H2 collisions in the presence of an external magnetic field using a recent ab initio potential energy surface. We find that the low-field-seeking states of H2 predominantly undergo elastic collisions: the ratio of elastic-to-inelastic cross sections exceeds 100 for collision energies below 100 mK. Furthermore, we demonstrate that most inelastic collisions conserve the space-fixed projection of the nuclear spin. We show that the anisotropic hyperfine interaction between the nuclear spin of H2 and the electron spin of Li can have a significant effect on inelastic scattering in the ultracold regime, as it mediates two processes: the electron spin relaxation in lithium and the nuclear spin-electron spin exchange. Given the predominance of elastic collisions and the propensity of inelastic collisions to retain H2 in its low-field-seeking states, our results open up the possibility of sympathetic cooling of molecular hydrogen by atomic lithium, paving the way for future exploration of ultracold collisions and high-precision spectroscopy of H2 molecules.

arXiv:2312.13652•The Journal of Chemical Physics•Mar 5, 2024•2 citations

Rovibrational energy levels of H$_2$O by quantum computing

Erik Lötstedt, Tamás Szidarovszky

We calculate rovibrational energy levels of H$_2$O using a trapped-ion quantum computer. We first derive the qubit form of Watson's Hamiltonian, including the rovibrational coupling terms. In a second step, we employ a variant of the quantum-selected configuration-interaction method to calculate rovibrational energy levels. A truncated form of the qubit Hamiltonian is used to generate correlated rovibrational wave functions on the quantum computer by time evolution, and a basis set is selected by sampling from the measured probability distribution. The rovibrational energy levels are obtained by constructing a Hamiltonian matrix using the selected basis set, and diagonalizing the matrix using a classical computer. We show that an accuracy of a few $hc$ cm$^{-1}$ can be achieved for low-lying rovibrational energy levels.

quant-pharXiv:2603.05795•The Journal of Chemical Physics•Mar 9, 2026•1 citation
Rovibrational energies, wave functions, and Raman transition moments are reported for the lowest-energy states of the H_{3}^{+} molecular ion including the magnetic couplings of the proton spins and molecular rotation in the presence of a weak external magnetic field. The rovibrational-hyperfine-Zeeman Hamiltonian matrix is constructed and diagonalized using the rovibrational eigenstates and the proton spin functions. The developed methodology can be used to compute hyperfine-Zeeman effects also for higher-energy rovibrational excitations of H_{3}^{+} and other closed-shell polyatomic molecules. These developments will guide future experiments extending quantum logic spectroscopy to polyatomic systems.
In the absence of experimental data for molecular spectra in strong magnetic fields, high resolution and reliable computational spectra are required for the interpretation of spectra collected from highly magnetic astrophysical objects. In this paper, we extend the Wilson-Hamiltonian framework, recently implemented and benchmarked by us (\textit{J. Chem. Theory Comput.}, \textbf{21}, 9753 (2025) ), to a general three-dimensional framework suitable for computing the rovibrational spectra of diatomic molecules in strong uniform magnetic fields. The field-dependent electronic and nuclear Hamiltonians capture full non-perturbative coupling between particle motion and the field making the method applicable to all field strengths. The electric quadrupole transition moment integrals for rovibrational transitions in external static magnetic fields are formulated, implemented, and computed to yield spectra which respect the selection rules of the molecule-field system. The spectral changes with increasing field strength such as shifting, splitting, merging, appearance and disappearance of peaks are noted. Contributions from electrons and nuclei are studied individually, as well as in unison to reveal the underlying physics such as stiffening of the bond, emergence of a rotational barrier, field-induced coupling/decoupling of states, and symmetry-breaking in rotational and vibrational states. These results provide the first fully quantum mechanical computational results for the rovibrational signature of 1H2^1\mathrm{H}_{2}1H2​ in extreme magnetic field environments with accuracy suitable for experimental interpretation. The methodology developed herein has direct relevance for high-field spectroscopy and astrochemical modeling, both for providing computational data as well as for understanding the spectral impact of strong magnetic fields on electronic structure and nuclear motion in molecules.
Cold collisions of polyatomic molecular radicals with S-state atoms in a magnetic field: An ab initio study of He + CH2(X~){\rm CH}_2(\tilde{X})CH2​(X~) CH 2(X) collisions
We develop a rigorous quantum mechanical theory for collisions of polyatomic molecular radicals with S-state atoms in the presence of an external magnetic field. The theory is based on a fully uncoupled space-fixed basis set representation of the multichannel scattering wave function. Explicit expressions are presented for the matrix elements of the scattering Hamiltonian for spin-1/2 and spin-1 polyatomic molecular radicals interacting with structureless targets. The theory is applied to calculate the cross sections and thermal rate constants for spin relaxation in low-temperature collisions of the prototypical organic molecule methylene [CH(2)(X(3)B(1))] with He atoms. To this end, two accurate three-dimensional potential energy surfaces (PESs) of the He-CH(2)(X(3)B(1)) complex are developed using the state-of-the-art coupled-cluster method including single and double excitations along with a perturbative correction for triple excitations and large basis sets. Both PESs exhibit shallow minima and are weakly anisotropic. Our calculations show that spin relaxation in collisions of CH(2), CHD, and CD(2) molecules with He atoms occurs at a much slower rate than elastic scattering over a large range of temperatures (1 μK-1 K) and magnetic fields (0.01-1 T), suggesting excellent prospects for cryogenic helium buffer-gas cooling of ground-state ortho-CH(2)(X(3)B(1)) molecules in a magnetic trap. Furthermore, we find that ortho-CH(2) undergoes collision-induced spin relaxation much more slowly than para-CH(2), which indicates that magnetic trapping can be used to separate nuclear spin isomers of open-shell polyatomic molecules.
Rovibrational structure and electric dipole moments of the AcOCH3_33​+ ion
The possibility of laser cooling and the presence of closely spaced rovibrational doublets make polyatomic molecules an attractive platform for the P\mathcal{P}P, T\mathcal{T}T-violation searches. We study the spectrum of the lowest rovibrational state of the AcOCH3+_3+3​+ symmetric top molecule. The electronic structure full-electron computation was performed within a relativistic coupled cluster method with double and perturbative triple excitations. The rovibrational wavefunctions are obtained using a coupled channel technique, taking into account all rovibrational effects and anharmonicities of the potential. As a result, the vibrational frequencies, as well as the values of the electric dipole moments for the rovibrational states, were computed.
In this work, we demonstrate a new method for quantum state control and nondestructive internal quantum state readout of a single HD^{+} ion in the rovibrational ground state in a Penning trap. Furthermore, we demonstrate a measurement of the magnetic trapping field with the same ion to sub-ppb uncertainty. This could enable nondestructive, high-precision spectroscopy of the hyperfine, Zeeman, and rovibrational level structure of single molecular ions. In particular, this technique can be applied to H_{2}^{+} as well as to its antimatter equivalent, H[over ¯]_{2}^{-}, with the potential for high-precision tests of charge-parity-time reversal symmetry beyond current sensitivities [Phys. Scr. T 1995, 423 (1995)PHSTBO0031-894910.1088/0031-8949/1995/T59/060, Phys. Rev. A 98, 010101 (2018)PLRAAN2469-992610.1103/PhysRevA.98.010101].
We present a rigorous quantum scattering study of the effects of hyperfine and Zeeman interactions on cold Li-H2 collisions in the presence of an external magnetic field using a recent ab initio potential energy surface. We find that the low-field-seeking states of H2 predominantly undergo elastic collisions: the ratio of elastic-to-inelastic cross sections exceeds 100 for collision energies below 100 mK. Furthermore, we demonstrate that most inelastic collisions conserve the space-fixed projection of the nuclear spin. We show that the anisotropic hyperfine interaction between the nuclear spin of H2 and the electron spin of Li can have a significant effect on inelastic scattering in the ultracold regime, as it mediates two processes: the electron spin relaxation in lithium and the nuclear spin-electron spin exchange. Given the predominance of elastic collisions and the propensity of inelastic collisions to retain H2 in its low-field-seeking states, our results open up the possibility of sympathetic cooling of molecular hydrogen by atomic lithium, paving the way for future exploration of ultracold collisions and high-precision spectroscopy of H2 molecules.
Rovibrational energy levels of H2_22​O by quantum computing
We calculate rovibrational energy levels of H2_22​O using a trapped-ion quantum computer. We first derive the qubit form of Watson's Hamiltonian, including the rovibrational coupling terms. In a second step, we employ a variant of the quantum-selected configuration-interaction method to calculate rovibrational energy levels. A truncated form of the qubit Hamiltonian is used to generate correlated rovibrational wave functions on the quantum computer by time evolution, and a basis set is selected by sampling from the measured probability distribution. The rovibrational energy levels are obtained by constructing a Hamiltonian matrix using the selected basis set, and diagonalizing the matrix using a classical computer. We show that an accuracy of a few hchchc cm−1^{-1}−1 can be achieved for low-lying rovibrational energy levels.