High Magnetic Field Detunes Vibronic Resonances in Photosynthetic Light Harvesting

MAIURI, MARGHERITA; OVIEDO, MARIA B.; DEAN, JACOB C.; BISHOP, MICHAEL; KUDISCH, BRYAN; TOA, ZI S. D.; WONG, BRYAN M.; MCGILL, STEPHEN A.; SCHOLES, GREGORY D.

Journal of Physical Chemistry Letters

American Chemical Society

Año: 2018 vol. 9 p. 5548 - 5554

The origin and role of oscillatory features detected in recent femtosecond spectroscopy experiments of photosynthetic complexes remain elusive. A key hypothesis underneath of these observations relies on electronic-vibrational resonance, where vibrational levels of an acceptor chromophore match the donor-acceptor electronic gap, accelerating the downhill energy transfer. Here we identify and detune such vibronic resonances using a high magnetic field that exclusively shifts molecular exciton states. We implemented ultrafast pump-probe spectroscopy into a specialized 25 T magnetic field facility and studied the light-harvesting complex PC645 from a cryptophyte algae where strongly coupled chromophores form molecular exciton states. We detected a change in high-frequency coherent oscillations when the field was engaged. Quantum chemical calculations coupled with a vibronic model explain the experiment as a magnetic field-induced shift of the exciton states, which in turn affects the electronic-vibrational resonance between pigments within the protein. Our results demonstrate the delicate sensitivity of interpigment coherent oscillations of vibronic origin to electronic-vibrational resonance interactions in light-harvesting complexes.