We revise the interpretation of coherence signals in photosynthetic systems and clarify what they tell us about light harvesting.

Vibrational quantum dynamics of conical intersection mediating singlet fission provides mechanistic insight on a structural level.

The success of organic-inorganic perovskites in optoelectronics is dictated by the complex interplay between various underlying microscopic phenomena. The structural dynamics of organic cations and the inorganic sublattice after photoexcitation is hypothesized to have a direct effect on the material properties, thereby affecting the overall device performance. Here, we use ultrafast heterodyne-detected two-dimensional (2D) electronic spectroscopy to reveal impulsively excited vibrational modes of methylammonium (MA) lead iodide perovskite, which drive the structural distortion after photoexcitation. The vibrational analysis of the measured data allows us to monitor the time-evolved librational motion of the MA cation along with the vibrational coherences of inorganic sublattice. Wavelet analysis of the observed vibrational coherences reveals the coherent generation of the librational motion of the MA cation within ~300 fs complemented with the coherent evolution of the inorganic skeletal motion. To rationalize this observation, we have employed the configuration interaction singles (CIS), which support our experimental observations of the coherent generation of librational motions in the MA cation and highlight the importance of the anharmonic interaction between the MA cation and the inorganic sublattice. Moreover, our advanced theoretical calculations predict the transfer of the photoinduced vibrational coherence from the MA cation to the inorganic sublattice leading to reorganization of the lattice to form a polaronic state with a long lifetime. Our study uncovers the interplay of the organic cation and inorganic sublattice during the formation of the polaron, which may lead to novel design principles for the next generation of perovskite solar cell materials.

Doping is an extremely important process where intentional insertion of impurities in semiconductors controls their electronic properties. In organic semiconductors, one of the convenient, but inefficient, ways of doping is the spin casting of a precursor mixture of components in solution, followed by solvent evaporation. Active control over this process holds the key to significant improvements over current poor doping efficiencies. Yet, an optimized control can only come from a detailed understanding of electronic interactions responsible for the low doping efficiencies. Here, we use two-dimensional nonlinear optical spectroscopy to examine these interactions in the course of the doping process by probing the solution mixture of doped organic semiconductors. A dopant accepts an electron from the semiconductor and the two ions form a duplex of interacting charges known as ion-pair complexes. Well-resolved off-diagonal peaks in the two-dimensional spectra clearly demonstrate the electronic connectivity among the ions in solution. This electronic interaction represents a well resolved electrostatically bound state, as opposed to a random distribution of ions. We developed a theoretical model to recover the experimental data, which reveals an unexpectedly strong electronic coupling of ∼250 cm⁻¹ with an intermolecular distance of ∼4.5 Å between ions in solution, which is approximately the expected distance in processed films. The fact that this relationship persists from solution to the processed film gives direct evidence that Coulomb interactions are retained from the precursor solution to the processed films. This memory effect renders the charge carriers equally bound also in the film and, hence, results in poor doping efficiencies. This new insight will help pave the way towards rational tailoring of the electronic interactions to improve doping efficiencies in processed organic semiconductor thin films.

Photosystem II (PSII) reaction center (RC) is a unique complex that is capable of efficiently separating electronic charges across the membrane. The primary energy- and charge-transfer (CT) processes occur on comparable ultrafast timescales, which makes it extremely challenging to understand the fundamental mechanism responsible for the near-unity quantum efficiency of the transfer. Here, we elucidate the role of quantum coherences in the ultrafast energy and CT in the PSII RC by performing two-dimensional (2D) electronic spectroscopy at the cryogenic temperature of 20 kelvin, which captures the distinct underlying quantum coherences. Specifically, we uncover the electronic and vibrational coherences along with their lifetimes during the primary ultrafast processes of energy and CT. We construct an excitonic model that provides evidence for coherent energy and CT at low temperature in the 2D electronic spectra. The principles could provide valuable guidelines for creating artificial photosystems with exploitation of system-bath coupling and control of coherences to optimize the photon conversion efficiency to specific functions.

This review critically explores quantum coherence and dissipation in photosynthetic protein complexes, revealing how system–bath interactions, rather than long-lived coherence, govern robust and efficient downhill energy transfer.