Ab Initio Rovibrational Spectroscopy of the Acetylide Anion

Abstract

In this work the rovibrational spectrum of the acetylide anion HCC− is investigated using high-level electronic structure methods and variational rovibrational calculations. Using a composite approach the potential energy surface and dipole surface is constructed from explicitly correlated coupled-cluster accounting for corrections due to core-valence correlation, scalar relativistic effects and higher-order excitation effects. Previous approaches for approximating the latter are critically evaluated. Employing the composite potential, accurate spectroscopic parameters determined from variational calculations are presented. In comparison to the few available reference data the present results show excellent agreement with ground state rotational constants within 0.005% of the experimental value. Intensities determined from the variational calculations suggest the bending fundamental transition ν2 around 510 cm−1 to be the best target for detection. The rather weak CD stretching fundamental ν1 in deuterated isotopologues show a second-order resonance with the (0,20,1) state and the consequences are discussed in some detail. The spectroscopic parameters and band intensities provided for a number of vibrational bands in isotopologues of the acetylide anion should facilitate future spectroscopic investigations.

Keywords

• acetylide anion
• potential energy surface
• variational calculations
• rovibrational spectrum
• spectroscopic parameters