Konstantin E. Dorfman

Quantum heat engine power can be increased by noise-induced coherence

Laser and photocell quantum heat engines (QHEs) are powered by thermal light and governed by the laws of quantum thermodynamics. To appreciate the deep connection between quantum mechanics and thermodynamics we need only recall that in 1901 Planck introduced the quantum of action to calculate the entropy of thermal light, and in 1905 Einstein’s studies of the entropy of thermal light led him to introduce the photon. Then in 1917, he discovered stimulated emission by using detailed balance arguments. Half a century later, Scovil and Schulz-DuBois applied detailed balance ideas to show that maser photons were produced with Carnot quantum efficiency (see Fig. 1A). Furthermore, Shockley and Quiesser invoked detailed balance to obtain the efficiency of a photocell illuminated by “hot” thermal light (see Fig. 2A). To understand this detailed balance limit, we note that in the QHE, the incident light excites electrons, which can then deliver useful work to a load. However, the efficiency is limited by radiative recombination in which the excited electrons are returned to the ground state. But it has been proven that radiatively induced quantum coherence can break detailed balance and yield lasing without inversion. Here we show that noise-induced coherence enables us to break detailed balance and get more power out of a laser or photocell QHE. Surprisingly, this coherence can be induced by the same noisy (thermal) emission and absorption processes that drive the QHE (see Fig. 3A). Furthermore, this noise-induced coherence can be robust against environmental decoherence.Fig. 1. (A) Schematic of a laser pumped by hot photons at temperature Th (energy source, blue) and by cold photons at temperature Tc (entropy sink, red). The laser emits photons (green) such that at threshold the laser photon energy and pump photon energy is related by Carnot efficiency (4). (B) Schematic of atoms inside the cavity. Lower level b is coupled to the excited states a and β. The laser power is governed by the average number of hot and cold thermal photons, and

Photosynthetic reaction center as a quantum heat engine

Two seemingly unrelated effects attributed to quantum coherence have been reported recently in natural and artificial light-harvesting systems. First, an enhanced solar cell efficiency was predicted and second, population oscillations were measured in photosynthetic antennae excited by sequences of coherent ultrashort laser pulses. Because both systems operate as quantum heat engines (QHEs) that convert the solar photon energy to useful work (electric currents or chemical energy, respectively), the question arises whether coherence could also enhance the photosynthetic yield. Here, we show that both effects arise from the same population–coherence coupling term which is induced by noise, does not require coherent light, and will therefore work for incoherent excitation under natural conditions of solar excitation. Charge separation in light-harvesting complexes occurs in a pair of tightly coupled chlorophylls (the special pair) at the heart of photosynthetic reaction centers of both plants and bacteria. We show the analogy between the energy level schemes of the special pair and of the laser/photocell QHEs, and that both population oscillations and enhanced yield have a common origin and are expected to coexist for typical parameters. We predict an enhanced yield of 27% in a QHE motivated by the reaction center. This suggests nature-mimicking architectures for artificial solar energy devices.

Quantum-coherence-enhanced surface plasmon amplification by stimulated emission of radiation.

We investigate surface plasmon amplification in a silver nanoparticle coupled to an externally driven three-level gain medium and show that quantum coherence significantly enhances the generation of surface plasmons. Surface plasmon amplification by stimulated emission of radiation is achieved in the absence of population inversion on the spasing transition, which reduces the pump requirements. The coherent drive allows us to control the dynamics and holds promise for quantum control of nanoplasmonic devices.

Catching Conical Intersections in the Act: Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals

Conical intersections (CIs) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CIs have not been directly observed yet and the experimental evidence is being inferred from fast reaction rates and some vibrational signatures. We show that short x-ray (rather than optical) pulses can directly detect the passage through a CI with the adequate temporal and spectral sensitivity. The technique is based on a coherent Raman process that employs a composite femtosecond or attosecond x-ray pulse to detect the electronic coherences (rather than populations) that are generated as the system passes through the CI.

Probing the Conical Intersection Dynamics of the RNA Base Uracil by UV-Pump Stimulated-Raman-Probe Signals; Ab Initio Simulations

Nonadiabatic electron and nuclear dynamics of photoexcited molecules involving conical intersections is of fundamental importance in many reactions such as the self-protection mechanism of DNA and RNA bases against UV irradiation. Nonlinear vibrational spectroscopy can provide an ultrafast sensitive probe for these processes. We employ a simulation protocol that combines nonadiabatic on-the-fly molecular dynamics with a mode-tracking algorithm for the simulation of femtosecond stimulated Raman spectroscopy (SRS) signals of the high frequency C–H- and N–H-stretch vibrations of the photoexcited RNA base uracil. The simulations rely on a microscopically derived expression that takes into account the path integral of the excited state evolution and the pulse shapes. Analysis of the joint time/frequency resolution of the technique reveals a matter chirp contribution that limits the inherent temporal resolution. Characteristic signatures of relaxation dynamics mediated in the vicinity of conical intersection are predicted. The C–H and N–H spectator modes provide high sensitivity to their local environment and act as local probes with submolecular and high temporal resolution.

Suppression of population transport and control of exciton distributions by entangled photons.

Entangled photons provide an important tool for secure quantum communication, computing and lithography. Low intensity requirements for multi-photon processes make them idealy suited for minimizing damage in imaging applications. Here we show how their unique temporal and spectral features may be used in nonlinear spectroscopy to reveal properties of multiexcitons in chromophore aggregates. Simulations demostrate that they provide unique control tools for two-exciton states in the bacterial reaction centre of Blastochloris viridis. Population transport in the intermediate single-exciton manifold may be suppressed by the absorption of photon pairs with short entanglement time, thus allowing the manipulation of the distribution of two-exciton states. The quantum nature of the light is essential for achieving this degree of control, which cannot be reproduced by stochastic or chirped light. Classical light is fundamentally limited by the frequency-time uncertainty, whereas entangled photons have independent temporal and spectral characteristics not subjected to this uncertainty.

Time-resolved broadband Raman spectroscopies: A unified six-wave-mixing representation

Excited-state vibrational dynamics in molecules can be studied by an electronically off-resonant Raman process induced by a probe pulse with variable delay with respect to an actinic pulse. We establish the connection between several variants of the technique that involve either spontaneous or stimulated Raman detection and different pulse configurations. By using loop diagrams in the frequency domain, we show that all signals can be described as six wave mixing which depend on the same four point molecular correlation functions involving two transition dipoles and two polarizabilities and accompanied by a different gating. Simulations for the stochastic two-state-jump model illustrate the origin of the absorptive and dispersive features observed experimentally.

Femtosecond Stimulated Raman Spectroscopy of the Cyclobutane Thymine Dimer Repair Mechanism: A Computational Study

Cyclobutane thymine dimer, one of the major lesions in DNA formed by exposure to UV sunlight, is repaired in a photoreactivation process, which is essential to maintain life. The molecular mechanism of the central step, i.e., intradimer C—C bond splitting, still remains an open question. In a simulation study, we demonstrate how the time evolution of characteristic marker bands (C=O and C=C/C—C stretch vibrations) of cyclobutane thymine dimer and thymine dinucleotide radical anion, thymidylyl(3′→5′)thymidine, can be directly probed with femtosecond stimulated Raman spectroscopy (FSRS). We construct a DFT(M05-2X) potential energy surface with two minor barriers for the intradimer C5—C5′ splitting and a main barrier for the C6—C6′ splitting, and identify the appearance of two C5=C6 stretch vibrations due to the C6—C6′ splitting as a spectroscopic signature of the underlying bond splitting mechanism. The sequential mechanism shows only absorptive features in the simulated FSRS signals, whereas the fast concerted mechanism shows characteristic dispersive line shapes.

Simulating Coherent Multidimensional Spectroscopy of Nonadiabatic Molecular Processes: From the Infrared to the X-ray Regime

Crossings of electronic potential energy surfaces in nuclear configuration space, known as conical intersections, determine the rates and outcomes of a large class of photochemical molecular processes. Much theoretical progress has been made in computing strongly coupled electronic and nuclear motions at different levels, but how to incorporate them in different spectroscopic signals and the approximations involved are less established. This will be the focus of the present review. We survey a wide range of time-resolved spectroscopic techniques which span from the infrared to the X-ray regimes and can be used for probing the nonadiabatic dynamics in the vicinity of conical intersections. Transient electronic and vibrational probes and their theoretical signal calculations are classified by their information content. This includes transient vibrational spectroscopic methods (transient infrared and femtosecond off-resonant stimulated Raman), resonant electronic probes (transient absorption and photoelectron spectroscopy), and novel stimulated X-ray Raman techniques. Along with the precise definition of what to calculate for predicting the various signals, we outline a toolbox of protocols for their simulation.

Manipulation of two-photon-induced fluorescence spectra of chromophore aggregates with entangled photons: A simulation study

The nonclassical spectral and temporal features of entangled photons offer new possibilities to investigate the interactions of excitons in photosynthetic complexes and to target the excitation of specific states. Simulations of fluorescence in the bacterial reaction center induced by entangled light demonstrate a degree of selectivity of double-exciton states which is not possible using classical stochastic light with the same power spectrum.