Calculation of Electric Quadrupole Linestrengths for Diatomic Molecules: Application to the H2, CO, HF and O2 Molecules

Abstract

We present a unified variational treatment of the electric quadrupole (E2) matrix elements, Einstein coefficients, and line strengths 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 $^1\text{H}_2$ available in the literature. We also present accurate electronic structure calculations of the electric quadrupole moment functions for the $X^1Σ^+$ electronic states of $\text{CO}$ and $\text{HF}$ at the CCSD(T) and MRCI levels of theory, respectively, as well for the $a^1Δ_g$ -- $b^1Σ_g^+$ quadrupole transition moment of $\text{O}_2$ with MRCI level of theory. Accurate infrared E2 line lists for $^{12}\text{C}^{16}\text{O}$ and $^1\text{H}^{19}\text{F}$ are provided. A demonstration of spectroscopic applications is presented by simulating E2 spectra for $^{12}\text{C}^{16}\text{O}$, $\text{H}^{19}\text{F}$ and $^{16}\text{O}_2$ (Noxon $a^1Δ_g$ -- $b^1Σ_g^+$ band).