A Method for the Variational Calculation of Hyperfine-Resolved Rovibronic Spectra of Diatomic Molecules

[Image: see text] An algorithm for the calculation of hyperfine structure and spectra of diatomic molecules based on the variational nuclear motion is presented. The 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 wave functions are obtained for a given set of potential energy curves and associated couplings by a variation solution of the nuclear-motion Schrödinger equation. Fully hyperfine-resolved parity-conserved rovibronic Hamiltonian matrices for a given final angular momentum, F, are constructed and then diagonalized to give hyperfine-resolved energies and wave functions. 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 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 by the well-used effective Hamiltonian code PGOPHER.