Vladimir I. Novoderezhkin’s research while affiliated with Lomonosov Moscow State University and other places

We describe the new method that can be useful for calculation of the excitation dynamics in large molecular arrays that can be split into compartments with weak exciton coupling between them. In this method, the dynamics within each compartment is evaluated nonperturbatively using hierarchical equations of motion (HEOM), whereas transfers between the exciton states belonging to different compartments are treated by the generalized Förster (gF) theory. In a combined HEOM-gF approach, the number of equations increases linearly when adding new compartments as opposed to pure HEOM, where a depth of hierarchy exhibits strong non-linear grows when scaling the total number of molecules. Comparing the combined HEOM-gF method with an exact HEOM solution enabled us to estimate the parameters corresponding to a validity range of the proposed theory. The possibility of using the method for modeling of energy transfers in photosynthetic antenna supercomplexes is discussed.

We perform theoretical studies of nonlinear spectral responses of molecular aggregates upon multiple electronic excitations. It is shown that the transient absorption (TA) spectra exhibit gradual shifting to short wavelengths...

We explore the energy equilibration within the LHCII trimer using various approaches, including the Redfield-Förster method (with different compartmentalization schemes) and the exact hierarchical equation of motion (HEOM). We demonstrate that the inter-monomeric migration in the trimeric LHCII complex is not limited to direct transfers between quasi-equilibrated chlorophylls (Chls) a, but also involves additional pathways with uphill transfers from Chls a to the stromal-side Chls b (connecting the Chls a clusters from different monomeric subunits). Although these uphill transfers are slow they still can increase the total rate of inter-monomeric transfers by a factor of 1.5. The same stromal-side Chls b also promote a depopulation of the Chl a604 long-lived state (blue-shifted and mixed with the lumenal-side Chls b). Due to the connection between the stromal- and lumenal-side Chls b clusters the intra- and inter-monomeric transfers from a604 to the main Chls a become faster by a factor of 1.6 and 1.75, respectively.

Photosynthetic light-harvesting complexes usually contain several pools of molecules with a big difference in transition energies, for example, chlorophylls a and b in plant antennas. Some pathways of the excitation energy transfer may include pigments from the low-energy pool separated by a site occupied by a high-energy molecule. We demonstrate that such pathways may be functional if high-frequency intramolecular vibrations fall in resonance with the energy gap between the neighboring molecules belonging to different pools. In this case, a vibration-assisted mixing of the excited states can produce delocalized vibronic states playing a role of ‘quantum bridge’ that facilitates a passage over high-energy barrier. We perform calculations of the excitation dynamics in the model three-state system with the parameters emerging from our previous studies of real antennas. Simulation of the dynamics in an explicit electron-vibrational basis demonstrates that the rate of transfer between the two chlorophylls a through the chlorophyll b intermediate is increased by a factor of 1.7–2 in the presence of resonant vibration. A possible influence of energetic disorder and other (non-resonant) vibrations on this effect is discussed.

We develop the theory for the Stark fluorescence (SF) of molecular aggregates by taking into account the mixing of the excited states [including the states with charge-transfer (CT) characters]. We use the sum-over-state approach and modified rotating wave approximation to describe interactions of the static and optical fields with the permanent and transition dipoles of the excited states. The SF spectral profiles are calculated using the standard and modified Redfield theories for the emission lineshapes. The resulting expression allows an interpretation of the SF response based on the calculation of only one-exciton states (i.e., the calculation of two-exciton states is not needed). The shape and amplitude of the SF spectrum can exhibit dramatic changes in the presence of the CT states, especially when the CT state is mixed with the red-most emitting exciton levels. In this case, the SF responses are much more sensitive to the exciton-CT mixing as compared with the usual Stark absorption. The limitation of the proposed theory is related to the simplified nature of the Redfield picture, which neglects the dynamic localization within the mixed exciton-CT configuration.

We model the excitation dynamics in bacterial B850 antenna using the standard Redfield, modified Redfield, and Förster approaches and comparing them with the exact solution obtained with hierarchical equation of motion (HEOM). We have found that the modified Redfield is capable of reproducing the dynamics associated with downhill relaxation from higher exciton levels, but fails to explain the migration of quasi-equilibrated excitation over the B850 ring (and its spectral signatures like transient anisotropy decay). Neglecting the population-to-coherence transfers leads to a quick decoherence between the exciton states resulting in unrealistically fast delocalization looking like instantaneous transfer around the ring. The standard (non-secular) Redfield gives a more satisfactory picture of this kind of migration, but in some cases the results can be corrupted by artifacts emerging from the one-phonon character of this theory.

The linear 15-mer peptide gramicidin A (gA) produced by Bacillus brevis is known to form the simplest natural ion channel in lipid membranes representing a head-to-head transmembrane dimer. Its incorporation into a planar lipid bilayer manifests itself in regular electrical current transitions. If two gA subunits are tightly connected by a water-soluble, flexible linker of a certain length, the current transitions become heterogeneous: in a part of them, the amplitude is almost twofold higher than that of a single channel, thereby demonstrating the synchronous opening of two single channels. The lifetime, i.e. the open-state duration, of this dual channel is by several orders of magnitude longer than that of the single channel. Here, we used the ideas of the theory of excitons to hypothesize about the mechanism of synchronous opening and closing of two adjacent channels. Two independent (uncoupled) single channels can be described by two independent conformational coordinates q1 and q2, while two closely located channels can exhibit collective behavior, if the coupling between them produces mixing of the individual states (q1,0) and (0,q2). We suppose that a similar phenomenon can occur not only with synthetic derivatives of gA, but also with such natural channel-forming peptide antibiotics and toxins as alamethicin and syringomycin. In particular, channel clustering observed with these peptides may be also associated with formation of collective conductance states, resulting from mixing of their monomeric states, which allows us to explain the fact that clusters of these channels transmit ions and nonelectrolytes of the same size as the original single channels.

Lhca1 is one of the four pigment-protein complexes composing the outer antenna of plant Photosystem I-light-havesting I supercomplex (PSI-LHCI). It forms a functional dimer with Lhca4 but, differently from this complex, it does not contain ‘red-forms,’ i.e., pigments absorbing above 700 nm. Interestingly, the recent PSI-LHCI structures suggest that Lhca1 is the main point of delivering the energy harvested by the antenna to the core. To identify the excitation energy pathways in Lhca1, we developed a structure-based exciton model based on the simultaneous fit of the low-temperature absorption, linear dichroism, and fluorescence spectra of wild-type Lhca1 and two mutants, lacking chlorophylls contributing to the long-wavelength region of the absorption. The model enables us to define the locations of the lowest energy pigments in Lhca1 and estimate pathways and timescales of energy transfer within the complex and to the PSI core. We found that Lhca1 has a particular energy landscape with an unusual (compared to Lhca4, LHCII, and CP29) configuration of the low-energy states. Remarkably, these states are located near the core, facilitating direct energy transfer to it. Moreover, the low-energy states of Lhca1 are also coupled to the red-most state (red forms) of the neighboring Lhca4 antenna, providing a pathway for effective excitation energy transfer from Lhca4 to the core.

To uncover the mechanism behind the high photo-electronic conversion efficiency in natural photosynthetic complexes it is essential to trace the dynamics of electronic and vibrational quantum coherences. Here we apply wavelet analysis to two-dimensional electronic spectroscopy data for three purple bacterial reaction centers with mutations that produce drastically different rates of primary charge separation. From the frequency distribution and dynamic evolution features of the quantum beating, electronic coherence with a dephasing lifetime of ~50 fs, vibronic coherence with a lifetime of ~150 fs and vibrational/vibronic coherences with a lifetime of 450 fs are distinguished. We find that they are responsible for, or couple to, different specific steps during the primary charge separation process, i.e., intradimer charge transfer inside the special bacteriochlorophyll pair followed by its relaxation and stabilization of the charge-transfer state. The results enlighten our understanding of how quantum coherences participate in, and contribute to, a biological electron transfer reaction.