Monitoring polariton dynamics in the LHCII photosynthetic antenna in a microcavity by two-photon coincidence counting.

The relaxation dynamics of light-harvesting complex II in an optical cavity is explored theoretically by multidimensional photon coincidence counting spectroscopy. This technique reveals the dynamics in both single (e) and double (f) excitation bands. We study how the polariton dynamics are affected by coupling to photon modes and molecular vibrations described by a realistic spectral density at 77 K. Without the cavity, the e- and f-band energy transfer pathways are not clearly resolved due to the line broadening caused by fast exciton dephasing. The strong coupling to cavity photons results in well-resolved polariton modes. The hybrid nature of polaritons slows down their energy transfer rates.

State-selective excitation of the CO stretch in carboxyhemoglobin by mid-IR laser pulse shaping: a theoretical investigation.

We present simulations of the excitation of specific vibrational levels of the CO stretch in carboxyhemoglobin by shaped mid-IR laser pulses. The pulses are calculated using local control theory, adapted to account for the protein fluctuations, which are included using a microscopic model developed previously. We show that efficient selective vibrational state preparation can be obtained, despite the presence of the fluctuations and orientational averaging, and can be monitored using transient absorption spectra. The mid-IR pulses are found to be in a realistic intensity regime and might soon be available by IR pulse shaping. This opens the way to a direct monitoring of vibrational relaxation from individually prepared, high-lying vibrational states of complex systems.

Vibrational ladder climbing in carboxy-hemoglobin: effects of the protein environment.

We present simulations on vibrational ladder climbing in carboxy-hemoglobin. Motivated by recent experiments, we study the influence of different realistic pump probe parameters. To allow for a direct comparison with experimental results, transient absorption spectra obtained by a weak probe pulse following the strong, shaped pump pulse are calculated. The influence of the protein fluctuations is taken into account using a recently developed microscopic model. This model consists of a quantum Hamiltonian describing the CO vibration in carboxy-hemoglobin, together with a fluctuating potential, which is obtained by electronic structure calculation based on a large number of protein configurations. Using realistic pulse parameters, vibrational excitations to very high-lying states are possible, in qualitative agreement with experimental observations.