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

Non-Markovianity: initial correlations and nonlinear optical measurements.

By extending the response function approach developed in nonlinear optics, we analytically derive an expression for the non-Markovianity in the time evolution of a system in contact with a quantum mechanical bath, and find a close connection with the directly observable nonlinear optical response. The result indicates that memory in the bath-induced fluctuations rather than in the dissipation causes non-Markovianity. Initial correlations between states of the system and the bath are shown to be essential for a correct understanding of the non-Markovianity. These correlations are included in our treatment through a preparation function

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

Non-Markovian entanglement dynamics in the presence of system-bath coherence

A complete treatment of the entanglement of two-level systems, which evolves through the contact with a thermal bath, must include the fact that the system and the bath are not fully separable. Therefore, quantum coherent superpositions of system and bath states, which are almost never fully included in theoretical models, are invariably present when an entangled state is prepared experimentally. We show their importance for the time evolution of the entanglement of two qubits coupled to independent baths. In addition, our treatment is able to handle slow and low-temperature thermal baths.Comment: Accepted for publication in Phys. Rev. Lett

Modeling the Vibrational Dynamics and Nonlinear Infrared Spectra of Coupled Amide I and II Modes in Peptides

The amide vibrational modes play an important role in energy transport and relaxation in polypeptides and proteins and provide us with spectral markers for structure and structural dynamics of these macromolecules. Here, we present a detailed model to describe the dynamic properties of the amide I and amide II modes and the resulting linear and nonlinear spectra. These two modes have large oscillator strengths, and their mutual coupling plays an important role in their relaxation. Using first-principles calculations of NMA-d(7) and a dipeptide in a fluctuating bath described by molecular dynamics simulations, we model the frequencies of the local vibrations as well as the coupling between them. Both the coherent couplings and the fluctuations induced by contact with their environment are taken into account. We apply the resulting model of interacting fluctuating oscillators to study the collective vibrations and the partially coherent transport of vibrational energy through a model a-helix. We find that the instantaneous vibrations are delocalized over a few (up to four) amide units, while the coherences in the helix survive for 0.5-1 ps, leading to coherent transport on a similar time scale.</p

Simulation of photo-excited adenine in water with a hierarchy of equations of motion approach

We present a theoretical method to simulate the electronic dynamics and two-dimensional ultraviolet spectra of the nucleobase adenine in water. The method is an extension of the hierarchy of equation of motion approach to treat a model with one or more conical intersections. The application to adenine shows that a two-level model with a direct conical intersection between the optically bright state and the ground state, generating a hot ground state, is not consistent with experimental observations. This supports a three-level model for the decay of electronically excited adenine in water as was previously proposed in [Prokhorenko et al., J. Phys. Chem. Lett. 7, 4445 (2016)]

Energy transfer in structured and unstructured environments: Master equations beyond the Born-Markov approximations

We explore excitonic energy transfer dynamics in a molecular dimer system coupled to both structured and unstructured oscillator environments. By extending the reaction coordinate master equation technique developed by Iles-Smith et al. [Phys. Rev. A 90, 032114 (2014)], we go beyond the commonly used Born-Markov approximations to incorporate system-environment correlations and the resultant non-Markovian dynamical effects. We obtain energy transfer dynamics for both underdamped and overdamped oscillator environments that are in perfect agreement with the numerical hierarchical equations of motion over a wide range of parameters. Furthermore, we show that the Zusman equations, which may be obtained in a semiclassical limit of the reaction coordinate model, are often incapable of describing the correct dynamical behaviour. This demonstrates the necessity of properly accounting for quantum correlations generated between the system and its environment when the Born-Markov approximations no longer hold. Finally, we apply the reaction coordinate formalism to the case of a structured environment comprising of both underdamped (i.e., sharply peaked) and overdamped (broad) components simultaneously. We find that though an enhancement of the dimer energy transfer rate can be obtained when compared to an unstructured environment, its magnitude is rather sensitive to both the dimer-peak resonance conditions and the relative strengths of the underdamped and overdamped contributions