Reassessing the role and lifetime of Q _<i>x</i> in the energy transfer dynamics of chlorophyll <i>a</i>

Chlorophylls are photoactive molecular building blocks essential to most photosynthetic systems. They have comparatively simple optical spectra defined by states with near-orthogonal transition dipole moments, referred to as B _<i>x</i> and B _<i>y</i> in the blue/green spectral region, and Q _<i>x</i> and Q _<i>y</i> in the red. Underlying these spectra is a surprisingly complex electronic structure, where strong electronic-vibrational interactions are crucial to the description of state characters. Following photoexcitation, energy-relaxation between these states is extremely fast and connected to only modest changes in spectral shapes. This has pushed conventional theoretical and experimental methods to their limits and left the energy transfer pathway under debate. In this work, we address the electronic structure and photodynamics of chlorophyll <i>a</i> using polarization-controlled static - and ultrafast - optical spectroscopies. We support the experimental data analysis with quantum dynamical simulations and effective heat dissipation models. We find clear evidence for B → Q transfer on a timescale of ∼100 fs and identify Q _<i>x</i> signatures within fluorescence excitation and transient spectra. However, Q _<i>x</i> is populated only fleetingly, with a lifetime well below our ∼30 fs experimental time resolution. Outside of these timescales, the kinetics are determined by vibrational relaxation and cooling. Despite its ultrashort lifetime, our theoretical analysis suggests that Q _<i>x</i> plays a crucial role as a bridging state in B → Q energy transfer. In summary, our findings present a unified and consistent picture of chlorophyll relaxation dynamics based on ultrafast and polarization-resolved spectroscopic techniques supported by extensive theoretical models; they clarify the role of Q _<i>x</i> in the energy deactivation network of chlorophyll <i>a</i>.