Prathamesh M. Shenai

Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study.

Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.

Optimal Energy Transfer in Light-Harvesting Systems.

Photosynthesis is one of the most essential biological processes in which specialized pigment-protein complexes absorb solar photons, and with a remarkably high efficiency, guide the photo-induced excitation energy toward the reaction center to subsequently trigger its conversion to chemical energy. In this work, we review the principles of optimal energy transfer in various natural and artificial light harvesting systems. We begin by presenting the guiding principles for optimizing the energy transfer efficiency in systems connected to dissipative environments, with particular attention paid to the potential role of quantum coherence in light harvesting systems. We will comment briefly on photo-protective mechanisms in natural systems that ensure optimal functionality under varying ambient conditions. For completeness, we will also present an overview of the charge separation and electron transfer pathways in reaction centers. Finally, recent theoretical and experimental progress on excitation energy transfer, charge separation, and charge transport in artificial light harvesting systems is delineated, with organic solar cells taken as prime examples.

Thermal-gradient-induced interaction energy ramp and actuation of relative axial motion in short-sleeved double-walled carbon nanotubes

We investigate the phenomenon of actuation of relative linear motion in double-walled carbon nanotubes (DWNTs) resulting from a temperature gradient. Molecular dynamics simulations of DWNTs with short outer tube reveal that the outer tube is driven towards the cold end of the long inner tube. It is also found that the terminal velocity of the sleeve roughly depends linearly on the applied thermal gradient. We calculate the inter-tube interaction energy surface which is revealed to have a gradient depending upon the applied thermal gradient. Consequently, it is proposed that the origin of the thermophoretic motion of the outer tube may be attributed partially to the existence of such an energy gradient. A simple analytical model is presented accounting for the gradient in energy profile as well as the effect of biased thermal noise. It is shown that the proposed model predicts the dynamical behaviour of the long-time performance reasonably well.

Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A

We have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Qy, the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes. The time dependence of the normal mode velocities is determined by projecting instantaneous Cartesian velocities onto the normal mode vectors. Our analysis of the time evolution of the average mode energies uncovers that only a small subset of the medium-to-high frequency normal modes actively participate in the electronic relaxation processes. These active modes are characterized by the highest overlap with the nonadiabatic coupling vectors (NACRs) during the electronic transitions. Further statistical analysis of the nonadiabatic transitions reveals that the electronic and vibrational energy relaxation occurs via two distinct pathways with significantly different time scales on which the hopping from Soret to Qx occurs thereby dictating the overall dynamics. Furthermore, the NACRs corresponding to each of the transitions have been consistently found to be predominantly similar to a set of normal modes that vary depending upon the transition and the identified categories. Each pathway exhibits a differential time scale of energy transfer and also a differential set of predominant active modes. Our present analysis can be considered as a general approach allowing identification of a reduced subset of specific vibrational coordinates associated with nonradiative relaxation pathways. Therefore, it represents an adequate prior strategy that can particularly facilitates mixed quantum-classical approaches.

Sub-Ohmic spin-boson model with off-diagonal coupling: Ground state properties

We have carried out analytical and numerical studies of the spin-boson model in the sub-ohmic regime with the influence of both the diagonal and the off-diagonal coupling accounted for, via the Davydov D1 variational ansatz. While a second-order phase transition is known to be exhibited by this model in the presence of diagonal coupling only, we demonstrate the emergence of a discontinuous first order phase transition upon incorporation of the off-diagonal coupling. A plot of the ground state energy versus magnetization highlights the discontinuous nature of the transition between the isotropic (zero magnetization) state and nematic (finite magnetization) phases. We have also calculated the entanglement entropy and a discontinuity found at a critical coupling strength further supports the discontinuous crossover in the spin-boson model in the presence of off-diagonal coupling. It is further revealed via a canonical transformation approach that for the special case of identical exponents for the spectral densities of the diagonal and the off-diagonal coupling, there exists a continuous crossover from a single localized phase to doubly degenerate localized phase with differing magnetizations.

Applications of Principal Component Analysis (PCA) in Materials Science

Nowadays we are living in the information age with the fast development of computational technologies and modern facilities. Larger data sets are produced by experiments and computer simulations. In contrast to conventional scientific approaches where simple models are built to fit the data, automated procedures are urged to obtain insights into the core messages carried by the large volume of data.

Disorder Influenced Absorption Line Shapes of a Chromophore Coupled to Two-Level Systems

We have carried out a theoretical and numerical study of disorder-induced changes in the absorption line shape of a chromophore embedded in a host matrix. The stochastic sudden jump model is employed wherein the host matrix molecules are treated as noninteracting two-level systems (TLSs) occupying points on a three-dimensional lattice with randomly oriented dipole moments. By systematically controlling the degree of positional disorder (α) attributed to them, a perfectly crystalline (α = 0) or a glassy environment (α = 1) or a combination of the two is obtained. The interaction between the chromophore and the TLSs is assumed to be of the dipole-dipole form. With an increase in α, the broadening of the absorption line shape was found to follow a power-law behavior. More importantly, it is revealed in the long-time limit that the resultant line shape is Gaussian in the absence of disorder but transforms to Lorentzian for a completely disordered environment. For an arbitrarily intermediate value of α, the resultant line shape can be approximately fitted by a linear combination of Gaussian and Lorentzian components. The Lorentzian profile for the disordered medium is attributed to the chomophore-TLS pairs with vanishingly small separation between them.

Investigation of the effects of commensurability on friction between concentric carbon nanotubes

That a commensurate contact usually leads to greater friction than an incommensurate one is a commonly held view in nanotribology. However, this perception seems paradoxical as commensurability is found to have negligible effect on the energy dissipation in double-walled carbon nanotube (DWNT) based oscillators. Using molecular dynamics simulations, we investigate such a paradox from the viewpoint of the atomic origin of friction. It is revealed that the commensurability cannot have a pronounced effect on friction unless the intertube interaction strength and the energy corrugation exceed their critical values. Both the commensurate and incommensurate oscillators constructed from natural DWNTs with an intertube distance of about 3.4 Å, may thus exhibit similar performance.