A method for the variational calculation of hyperfine-resolved rovibronic spectra of diatomic molecules

Abstract

An algorithm for the calculation of hyperfine structure and spectra of diatomic molecules based on the variational nuclear motion is presented. Hyperfine coupling terms considered are Fermi-contact, nuclear spin-electron spin dipole-dipole, nuclear spin-orbit, nuclear spin-rotation and nuclear electric quadrupole interactions. Initial hyperfine-unresolved wavefunctions are obtained for given set of potential energy curves and associated couplings by variation solution of the nuclear-motion Schrödinger equation. Fully hyperfine-resolved parity-conserved rovibronic Hamiltonian matrices for a given final angular momentum, $\mathbf{F}$, are constructed and then diagonalized to give hyperfine-resolved energies and wavefunctions.Electric transition dipole moment curves can then be used to generate a hyperfine-resolved line list by applying rigorous selection rules.The algorithm is implemented in \textsc{Duo}, which is a general program for calculating spectra of diatomic molecules. This approach is tested for NO and MgH,and the results are compared to experiment and shown to be consistent with those given the well-used effective Hamiltonian code PGOPHER.

arXiv commentAccepted by Journal of Chemical Theory and Computation

References in corpus (20)

• Magneto-optical trapping of diatomic molecules
• ExoMol Molecular linelists -- XXXIII. The spectrum of Titanium Oxide
• The 2020 release of the ExoMol database: molecular line lists for exoplanet and other hot atmospheres
• ExoMol line lists XVIII. The high temperature spectrum of VO
• Duo: a general program for calculating spectra of diatomic molecules
• ExoMol molecular line lists: IX The spectrum of AlO
• Rotational state microwave mixing for laser cooling of complex diatomic molecules
• Non-detection of TiO and VO in the atmosphere of WASP-121b using high-resolution spectroscopy
• ExoMol molecular line lists - XIII: The spectrum of CaO
• The ExoMol project: Software for computing large molecular line lists
• ExoMol Line List XXI: Nitric Oxide (NO)
• The {\it ab initio} calculation of spectra of open shell diatomic molecules
• ExoMol line lists -- XLIV. IR and UV line list for silicon monoxide (SiO)
• Calculation of Electric Quadrupole Linestrengths for Diatomic Molecules: Application to the H2, CO, HF and O2 Molecules
• Hyperfine structure of the first rotational level in H${}_2$, D${}_2$ and HD molecules and the deuteron quadrupole moment
• Spectroscopy of YO from first principles
• ExoMol line lists -- XLV. Rovibronic molecular line lists of calcium monohydride (CaH) and magnesium monohydride (MgH)
• Excitation and characterization of long-lived hydrogenic Rydberg states of nitric oxide
• A spectroscopic model for the low-lying electronic states of NO
• Low temperature scattering with the R-matrix method: argon-argon scattering

Cited by in corpus (4)

• A variational model for the hyperfine resolved spectrum of VO in its ground electronic state
• ExoMol line lists -- LIII: Empirical Rovibronic spectra of Yttrium Oxide (YO)
• An empirical spectroscopic model for eleven electronic states of VO
• Nuclear Electric Quadrupole Moment-Induced Parity Doubling in Molecules for Symmetry-Violation Searches