Linear, third- and fifth-order nonlinear spectroscopy of a charge transfer system coupled to an underdamped vibration

We study hole, electron and exciton transport in a charge transfer system in the presence of underdamped vibrational motion. We analyze the signature of these processes in the linear and third-, and fifth-order nonlinear electronic spectra. Calculations are performed with a numerically exact hierarchical equations of motion method for an underdamped Brownian oscillator spectral density. We find that combining electron, hole and exciton transfer can lead to non-trivial spectra with more structure than with excitonic coupling alone. Traces taken during the waiting time of a two-dimensional spectrum are dominated by vibrational motion and do not reflect the electron, hole, and exciton dynamics directly. We find that the fifth-order nonlinear response is particularly sensitive to the charge transfer process. While third-order 2D spectroscopy detects the correlation between two coherences, fifth-order 2D spectroscopy (2D population spectroscopy) is here designed to detect correlations between the excited states during two different time periods

Correlated fluctuations in the exciton dynamics and spectroscopy of DNA

The absorption of ultraviolet light creates excitations in DNA, which subsequently start moving in the helix. Their fate is important for an understanding of photo damage, and is determined by the interplay of electronic couplings between bases and the structure of the DNA environment. We model the effect of dynamical fluctuations in the environment and study correlation, which is present when multiple base pairs interact with the same mode in the environment. We find that the correlations strongly affect the exciton dynamics, and show how they are observed in the decay of the anisotropy as a function of a coherence and a population time in a non-linear optical experiment

Predicting the Success of Invasive Species in the Great Bay Estuarine Researve

The University of New Hampshire Zoology Department reports on a study designed to continue monitoring the distribution of invasive species in the Great Bay Estuary and to carry out laboratory experiments designed to test the effects of salinity on ascidian mortality and determine predators of ascidian species. Researchers collected presence/absence and abundance data of invasive species at four sites within the Great Bay Estuarine System. The report gives a brief description of the results of the monitoring program to compare results obtained from 2006 to 2007 and to assess the response of ascidians to varying salinity and predators. This report specifically includes monitoring data from 2007 and results of laboratory and field experiments examining the effects of salinity and predators on ascidian distribution

Does settlement plate material matter? The influence of substrate type on fouling community development

Benthic community composition and ascidian abundance can differ dramatically between adjacent man-made and natural substrates. Although multiple factors, including light exposure, surface orientation, predation exposure, and habitat type, are known to contribute to these patterns, few studies have directly tested the influence of substrate identity on community development. We compared fouling communities on settlement plates composed of commonly occurring natural (granite) and artificial (concrete, high density polyethylene, and PVC) marine materials deployed from late May to mid November 2014 from a floating dock in Newcastle, NH. We sought to determine if observed patterns resulted from differential recruitment onto substrate materials or post-settlement survival and growth. To do this, half of the plates were cleaned during bi-weekly examinations, and half were left un-cleaned. Preliminary analyses indicate that community composition differs between substrate types. These results will help us understand how substrate features contribute to non-native species establishment and habitat dominance, and may inform decisions regarding material usage in marine construction. These findings also underline the importance of settlement substrate choice in scientific studies, as plate material may influence experimental conclusions

On finite-size Lyapunov exponents in multiscale systems

We study the effect of regime switches on finite size Lyapunov exponents (FSLEs) in determining the error growth rates and predictability of multiscale systems. We consider a dynamical system involving slow and fast regimes and switches between them. The surprising result is that due to the presence of regimes the error growth rate can be a non-monotonic function of initial error amplitude. In particular, troughs in the large scales of FSLE spectra is shown to be a signature of slow regimes, whereas fast regimes are shown to cause large peaks in the spectra where error growth rates far exceed those estimated from the maximal Lyapunov exponent. We present analytical results explaining these signatures and corroborate them with numerical simulations. We show further that these peaks disappear in stochastic parametrizations of the fast chaotic processes, and the associated FSLE spectra reveal that large scale predictability properties of the full deterministic model are well approximated whereas small scale features are not properly resolved.Comment: Accepted for publication in Chao

An efficient tool to calculate two-dimensional optical spectra for photoactive molecular complexes

We combine the coherent modified Redfield theory (CMRT) with the equation of motion-phase matching approach (PMA) to calculate two-dimensional photon echo spectra for photoactive molecular complexes with an intermediate strength of the coupling to their environment. Both techniques are highly efficient, yet they involve approximations at different levels. By explicitly comparing with the numerically exact quasi-adiabatic path integral approach, we show for the Fenna-Matthews-Olson complex that the CMRT describes the decay rates in the population dynamics well, but final stationary populations and the oscillation frequencies differ slightly. In addition, we use the combined CMRT+PMA to calculate two-dimensional photon-echo spectra for a simple dimer model. We find excellent agreement with the exact path integral calculations at short waiting times where the dynamics is still coherent. For long waiting times, differences occur due to different final stationary states, specifically for strong system-bath coupling. For weak to intermediate system-bath couplings, which is most important for natural photosynthetic complexes, the combined CMRT+PMA gives reasonable results with acceptable computational efforts

Coherent exciton dynamics in the presence of underdamped vibrations

Recent ultrafast optical experiments show that excitons in large biological light-harvesting complexes are coupled to molecular vibration modes. These high-frequency vibrations will not only affect the optical response, but also drive the exciton transport. Here, using a model dimer system, the frequency of the underdamped vibration is shown to have a strong effect on the exciton dynamics such that quantum coherent oscillations in the system can be present even in the case of strong noise. Two mechanisms are identified to be responsible for the enhanced transport efficiency: critical damping due to the tunable effective strength of the coupling to the bath, and resonance coupling where the vibrational frequency coincides with the energy gap in the system. The interplay of these two mechanisms determines parameters responsible for the most efficient transport, and these optimal control parameters are comparable to those in realistic light-harvesting complexes. Interestingly, oscillations in the excitonic coherence at resonance are suppressed in comparison to the case of an off-resonant vibration