Electronic Symmetry and Femtosecond Coherence Dynamics of Renner-Teller-Mixed Neutral Vibronic States in Carbon Dioxide

Abstract

When non-adiabatic coupling mixes electronic states of a molecule, vibronic states of different electronic symmetry become interleaved across the same spectral region. The symmetry of these states cannot be accessed in conventional spectroscopy due to orientation averaging. We show that molecular-frame angular signatures, which are preserved even when states with different symmetry overlap in energy, can be used to resolve them. Using vacuum-ultraviolet transient absorption spectroscopy of aligned carbon dioxide molecules, we separate two electronically distinct classes of vibronic states ($A^{'}$ and $A^{''}$) that arise from Renner-Teller splitting of the $^1Δ_u$ state. We reconstruct molecular-frame anisotropy continuously across the vibronic manifold showing that the anisotropy crosses over from perpendicular to parallel transition character and maps the interleaved electronic symmetry landscape. By scanning the femtosecond delay between the VUV and a near-infrared pulse through temporal overlap, we measure symmetry-dependent coherence dephasing times of these states and find that the parallel ($A^{'}$) states dephase faster than the perpendicular ($A^{''}$) states. We attribute this to faster departure of the $A^{'}$ wavepacket from the Franck-Condon region due to the distinct topology of the $A^{'}$ excited-state surface. These measurements probe symmetry-resolved ultrafast wavepacket dynamics on the coupled excited-state potential energy surfaces.