An ab initio study of the rovibronic spectrum of sulphur monoxide (SO): diabatic vs. adiabatic representation.

We present an ab initio study of the rovibronic spectra of sulphur monoxide (32S16O) using internally contracted multireference configuration interaction (ic-MRCI) method and aug-cc-pV5Z basis sets. It covers 13 electronic states X3Σ-, a1Δ, b1Σ+, c1Σ-, A''3Σ+, A'3Δ, A3Π, B3Σ-, C3Π, d1Π, e1Π, C'3Π, and (3)1Π ranging up to 66 800 cm-1. The ab initio spectroscopic model includes 13 potential energy curves, 23 dipole and transition dipole moment curves, 23 spin-orbit curves, and 14 electronic angular momentum curves. A diabatic representation is built by removing the avoided crossings between the spatially degenerate pairs C3Π-C'3Π and e1Π-(3)1Π through a property-based diabatisation method. We also present non-adiabatic couplings and diabatic couplings for these avoided crossing systems. All phases for our coupling curves are defined, and consistent, providing the first fully reproducible spectroscopic model of SO covering the wavelength range longer than 147 nm. Finally, an ab initio rovibronic spectrum of SO is computed.

Calculation of electric quadrupole linestrengths for diatomic molecules: Application to the H2, CO, HF, and O2 molecules.

We present a unified variational treatment of the electric quadrupole (E2) matrix elements, Einstein coefficients, and linestrengths for general open-shell diatomic molecules in the general purpose diatomic code Duo. Transformation relations between the Cartesian representation (typically used in electronic structure calculations) to the tensorial representation (required for spectroscopic applications) of the electric quadrupole moment components are derived. The implementation has been validated against accurate theoretical calculations and experimental measurements of quadrupole intensities of 1H2 available in the literature. We also present accurate electronic structure calculations of the electric quadrupole moment functions for the X1Σ+ electronic states of CO and HF, as well as for the a1Δg-b1Σg + quadrupole transition moment of O2 with the MRCI level of theory. Accurate infrared E2 line lists for 12C16O and 1H19F are provided. A demonstration of spectroscopic applications is presented by simulating E2 spectra for 12C16O, H19F, and 16O2 (Noxon a1Δg-b1Σg + band).