Experimental proof of strong $\Pi$-$\Sigma$ mixing in the Renner-Teller and Pseudo-Jahn-Teller affected CCH${}^{+}$ (${}^3\Pi$) ion

Abstract

The ethynyl radical cation, CCH${}^{+}$ (${}^3\Pi$), offers a unique system for fundamental spectroscopic studies of non-adiabatic effects due to its open-shell linear structure and the presence of a low-lying ${}^3{\Sigma }^{-}$ state, which induces notable perturbations in the (ro-)vibrational spectrum. To probe these effects, we recorded the broadband vibrational spectrum of CCH${}^{+}$ from 350-3450 cm${}^{-1}$ using leak-out spectroscopy. The spectrum reveals a complex splitting pattern in the CCH bending mode, attributed to Renner-Teller and pseudo-Jahn-Teller coupling effects between the ${}^3\Pi$ and ${}^3{\Sigma }^{-}$ electronic states. A three-state diabatic model, validated here against high-resolution IR data of the CH stretching mode, facilitated assignments within the broadband infrared (IR) spectrum, including an additional $\Pi$ vibronic feature observed in the aforementioned high-resolution spectrum. Our results highlight a pronounced sensitivity of the splitting pattern to the $\Pi$-$\Sigma$ energy gap, with couplings so large that even the zero-point vibrational motion of the bending vibration is sufficient to disrupt the vibronic structure of this ion. This compact ion, with strong coupling effects and high-quality spectroscopic data, serves as an exemplary system for evaluating non-adiabatic models.

24 pages, 5 figures. Supplementary information can be found on the journal webpage. In press in The Journal of Physical Chemistry Letters

References in corpus (5)

• Leak-out Spectroscopy, a universal method of action spectroscopy in cold ion traps
• High-resolution spectroscopy of the ${\nu }_3$ antisymmetric C-H stretch of C${}_2$H${}_2^{+}$ using leak-out action spectroscopy
• High Resolution Rovibrational and Rotational Spectroscopy of H${}_2$CCCH${}^{+}$
• High Resolution Overtone Spectroscopy of HNC${}^{+}$ and HCN${}^{+}$
• High-resolution ro-vibrational and rotational spectroscopy of the open-shell, linear CCH${}^{+}$ ion (${}^3\Pi$)