A vibrational action spectroscopic study of the Renner-Teller- and spin-orbit-affected cyanoacetylene radical cation HC3N

Kim Steenbakkers; Aravindh N Marimuthu; Britta Redlich; Gerrit C Groenenboom; Sandra Brünken

doi:10.1063/5.0135000

A vibrational action spectroscopic study of the Renner-Teller- and spin-orbit-affected cyanoacetylene radical cation HC₃N

J Chem Phys. 2023 Feb 28;158(8):084305. doi: 10.1063/5.0135000.

Authors

Kim Steenbakkers¹, Aravindh N Marimuthu¹, Britta Redlich¹, Gerrit C Groenenboom², Sandra Brünken¹

Affiliations

¹ FELIX Laboratory, Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands.
² Radboud University, Institute for Molecules and Materials, Nijmegen, The Netherlands.

PMID: 36859081
DOI: 10.1063/5.0135000

Abstract

The linear radical cation of cyanoacetylene, HC₃N⁺ (²Π), is not only of astrophysical interest, being the, so far undetected, cationic counterpart of the abundant cyanoaceteylene, but also of fundamental spectroscopic interest due to its strong spin-orbit and Renner-Teller interactions. Here, we present the first broadband vibrational action spectroscopic investigation of this ion through the infrared pre-dissociation (IRPD) method using a Ne tag. Experiments have been performed using the FELion cryogenic ion-trap instrument in combination with the FELIX free-electron lasers and a Laservision optical parametric oscillator/optical parametric amplifier system. The vibronic splitting patterns of the three interacting bending modes (ν₅, ν₆, ν₇), ranging from 180 to 1600 cm^-1, could be fully resolved revealing several bands that were previously unobserved. The associated Renner-Teller and intermode coupling constants have been determined by fitting an effective Hamiltonian to the experimental data, and the obtained spectroscopic constants are in reasonable agreement with previous photoelectron spectroscopy (PES) studies and ab initio calculations on the HC₃N⁺ ion. The influence of the attached Ne atom on the infrared spectrum has been investigated by ab initio calculations at the RCCSD(T)-F12a level of theory, which strongly indicates that the discrepancies between the IRPD and PES data are a result of the effects of the Ne attachment.