Electronic coherence effects in photosynthetic light harvesting

Photosynthetic light harvesting is a paradigmatic example for quantum effects in biology. In this work, we review studies on quantum coherence effects in the LH2 antenna complex from purple bacteria to demonstrate how quantum mechanical rules play important roles in the speedup of excitation energy transfer, the stabilization of electronic excitations, and the robustness of light harvesting in photosynthesis. Subsequently, we present our recent theoretical studies on exciton dynamical localization and excitonic coherence generation in photosynthetic systems. We apply a variational-polaron approach to investigate decoherence of exciton states induced by dynamical fluctuations due to system-environment interactions. The results indicate that the dynamical localization of photoexcitations in photosynthetic complexes is significant and imperative for a complete understanding of coherence and excitation dynamics in photosynthesis. Moreover, we use a simple model to investigate quantum coherence effects in intercomplex excitation energy transfer in natural photosynthesis, with a focus on the likelihoods of generating excitonic coherences during the process. Our model simulations reveal that excitonic coherence between acceptor exciton states and transient nonlocal quantum correlation between distant pairs of chromophores can be generated through intercomplex energy transfer. Finally, we discuss the implications of these theoretical works and important open questions that remain to be answered.     

Photochemical Creation of Fluorescent Quantum Defects in Semiconducting Carbon Nanotube Hosts

Quantum defects are an emerging class of synthetic single‐photon emitters that hold vast potential for near‐infrared imaging, chemical sensing, materials engineering, and quantum information processing. Herein, we show that it is possible to optically direct the synthetic creation of molecularly tunable fluorescent quantum defects in semiconducting single‐walled carbon nanotube hosts through photochemical reactions. By exciting the host semiconductor with light that resonates with its electronic transition, we find that halide‐containing aryl groups can covalently bond to the sp² carbon lattice. The introduced quantum defects generate bright photoluminescence that allows tracking of the reaction progress in situ. We show that the reaction is independent of temperature but correlates strongly with the photon energy used to drive the reaction, suggesting a photochemical mechanism rather than photothermal effects. This type of photochemical reactions opens the possibility to control the synthesis of fluorescent quantum defects using light and may enable lithographic patterning of quantum emitters with electronic and molecular precision.     

Accurate time-resolved laser spectroscopy on lithium atoms

The lifetime of the lithium 2p ² P states has been measured with high accuracy using the delayed coincidence technique with a continuous mode-locked dye laser as the source of the excitation light. The value 27.22 (0.20) ns was obtained. In addition, the hyperfine structure of the⁷Li 2p ² P _3/2 state, which can normally scarcely be resolved, has been studied by recording the slow quantum beats at zero field and the very fast beats in the Paschen-Back regime. New accurate values for the²³Na 3p ² P _3/2 state hyperfine structure constants are also presented.     

Effects of magnetic field and geometrical size on the interband light absorption in a quantum pseudodot system

We study in this paper the direct interband transitions in quantum pseudodot system under the influence of an external magnetic field. We obtain the analytical expressions for the light interband absorption coefficient and threshold frequency of absorption as the functions of applied magnetic field and geometrical size of quantum pseudodot system. We study the absorption threshold frequency (ATF) at small and high applied magnetic field and also as a function of size of quantum pseudodot. According to the results obtained from the present work, we find that (i) the ATF is linear at large magnetic field. (ii) It is nonlinear at small magnetic field. (iii) The ATF depends on the geometrical size of quantum pseudodot and decreases when the size of quantum pseudodot increases. Therefore, the magnetic field and quantum pseudodot size play important roles in the ATF.     

Coherence quantum beats in two-dimensional electronic spectroscopy

We study the coherence quantum beats in two-dimensional (2D) electronic spectroscopy of a coupled dimer system using a theoretical method based on a time-nonlocal quantum master equation and a recently proposed scheme for the evaluation of the third-order photon echo polarization [Gelin, M. F.; Egorova, D.; Domcek, W. J. Chem. Phys. 2005, 123, 164112]. The simulations show that the amplitude and peak shape beating in the 2D spectra is a result of the interplay between the rephasing and non-rephasing contributions to the 2D signals and can be used to elucidate the coherence dynamics in a multichromophoric system. In addition, the results suggest that the rephasing and non-rephasing 2D spectra contain complementary information, and a study of both of them could provide more dynamical information from 2D electronic spectroscopy.     

Ultrafast Auger Spectroscopy of Quantum Well Excitons in Strong Magnetic Fields

We study theoretically the ultrafast nonlinear optical response of quantum well excitons in a perpendicular magnetic field. We address the role of many-body correlations originating from the electron scattering between Landau levels (LL). In the linear optical response, the processes involving inter-LL transitions are suppressed provided that the magnetic field is sufficiently strong. However, in the nonlinear response, the Auger processes involving inter-LL scattering of two photoexcited electrons remain unsuppressed. We show that Auger scattering plays a dominant role in the coherent exciton dynamics in strong magnetic fields. We perform numerical calculations for the third-order four-wave-mixing (FWM) polarization, which incorporate the Auger processes nonperturbatively. We find that inter-LL scattering leads to a strong enhancement of FWM signal and to oscillations at negative time delays. These oscillations represent quantum beats between optically inactive two-exciton states related to each other via Auger processes.     

Influence of environment induced correlated fluctuations in electronic coupling on coherent excitation energy transfer dynamics in model photosynthetic systems

Two-dimensional photon-echo experiments indicate that excitation energy transfer between chromophores near the reaction center of the photosynthetic purple bacterium Rhodobacter sphaeroides occurs coherently with decoherence times of hundreds of femtoseconds, comparable to the energy transfer time scale in these systems. The original explanation of this observation suggested that correlated fluctuations in chromophore excitation energies, driven by large scale protein motions could result in long lived coherent energy transfer dynamics. However, no significant site energy correlation has been found in recent molecular dynamics simulations of several model light harvesting systems. Instead, there is evidence of correlated fluctuations in site energy-electronic coupling and electronic coupling-electronic coupling. The roles of these different types of correlations in excitation energy transfer dynamics are not yet thoroughly understood, though the effects of site energy correlations have been well studied. In this paper, we introduce several general models that can realistically describe the effects of various types of correlated fluctuations in chromophore properties and systematically study the behavior of these models using general methods for treating dissipative quantum dynamics in complex multi-chromophore systems. The effects of correlation between site energy and inter-site electronic couplings are explored in a two state model of excitation energy transfer between the accessory bacteriochlorophyll and bacteriopheophytin in a reaction center system and we find that these types of correlated fluctuations can enhance or suppress coherence and transfer rate simultaneously. In contrast, models for correlated fluctuations in chromophore excitation energies show enhanced coherent dynamics but necessarily show decrease in excitation energy transfer rate accompanying such coherence enhancement. Finally, for a three state model of the Fenna-Matthews-Olsen light harvesting complex, we explore the influence of including correlations in inter-chromophore couplings between different chromophore dimers that share a common chromophore. We find that the relative sign of the different correlations can have profound influence on decoherence time and energy transfer rate and can provide sensitive control of relaxation in these complex quantum dynamical open systems.     

Determination of asymmetry splittings in the polyatomic molecule propynal by Stark quantum beat spectroscopy

Coherences among asymmetry-split rotational levels in a molecule can be created when a weak electric field is applied. The quantum beats superimposed on the time-resolved fluorescence decay are utilized for the accurate measurement of asymmetry splittings. The technique is exemplified for selected vibronicS ₁ states of propynal and αD-propynal and the results are compared with conventional (i.e. frequency domain) spectroscopic data. The applicability of the presented method of coherence spectroscopy is discussed.     

Peak coalescence,spontaneous loss of coherence,and quantification of the relative abundances of two species in the plasma regime: Particle-in-cell modeling of fourier transform ion cyclotron resonance mass spectrometry

Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is often limited by space-charge effects. Previously, particle-in-cell (PIC) simulations have been used to understand these effects on FTICR-MS signals. However, none have extended fully into the space-charge dominated (plasma) regime. We use a two-dimensional (2-D) electrostatic PIC code, which facilitates work at very high number densities at modest computational cost to study FTICR-MS in the plasma regime. In our simulation, we have observed peak coalescence and the rapid loss of signal coherence, two common experimental problems. This demonstrates that a 2-D model can simulate these effects. The 2-D code can handle a larger numbers of particles and finer spatial resolution than can currently be addressed by 3-D models. The PIC method naturally takes into account image charge and space charge effects in trapped-ion mass spectrometry. We found we can quantify the relative abundances of two closely spaced (such as ⁷Be⁺ and ⁷Li⁺) species in the plasma regime even when their peaks have coalesced. We find that the frequency of the coalesced peak shifts linearly according to the relative abundances of these species. Space charge also affects more widely spaced lines. Singly-ionized ⁷BeH and ⁷Li have two separate peaks in the plasma regime. Both the frequency and peak area vary nonlinearly with their relative abundances. Under some conditions, the signal exhibited a rapid loss of coherence. We found that this is due to a high order diocotron instability growing in the ion cloud.     

Theory of ultrafast time-resolved absorption spectroscopy

In this paper, the density matrix formalism has been applied to treat ultrafast time-resolved absorption spectroscopy. We have shown that in the femto-second (fs) pump-probe experiments, the observed time-resolved absorption spectra consist of the contributions from the population (i.e., incoherent contribution) and the coherence (i.e., the phase of the system). The adiabatic approximation has been used to derive the expressions for ultrafast time-resolved spectra. We have also shown that the dynamics of the coherence will result in quantum beat. Numerical calculations have been performed to demonstrate the theoretical results.     

Quantum beat spectroscopy of zeeman splitting and level anticrossing of rotationally selected acetylene (Ã1Au3v3) under weak magnetic fields

New quantum beats have been observed in the fluorescence from a rotational level of the ùA_uv₃ = 3 state of acetylene in a weak magnetic field. The observed quantum beats could be classified into two categories; one due to Zeeman splitting of the relevant level, and the other due to magnetic field-induced level anticrossing between the à singlet level and a non-fluorescent level having a large magnetic moment.     

Memory effects on energy transport in substitutionally disordered molecular crystals

In this paper we consider the manifestations of coherence effects in electronic energy transport (EET) between randomly distributed donors. We have extended previous theoretical schemes for EET in an impurity band to incorporate a finite memory time for the EET. The short-time behaviour of the mean square displacement of the excitation. [x²(t)], and the initial-site survival probability, P₀(t), exhibit two distinct transport regimes: (i) A coherent regime at ultrashort times, where [x²(t)] ∝ t², and (ii) a partially coherent regime, which is characterized by [x²(t)] ∝ t^10/μ, where μ is the order of the multipolar transition rate, which is intermediate between coherent and conventional diffusive behaviour. Coherence effects also result in the retardation of the short-time decay of P₀(t). The short-time partially coherent transport regime may be amenable to experimental interrogation by utilizing sub-ps and fs laser excitation. On the time scale exceeding the memory time, the conventional dispersive diffusive behaviour and the subsequent onset of classical diffusion for EET are recovered.     

Exploiting clock transitions for the chemical design of resilient molecular spin qubits

Molecular spin qubits are chemical nanoobjects with promising applications that are so far hampered by the rapid loss of quantum information, a process known as decoherence. A strategy to improve this situation involves employing so-called Clock Transitions (CTs), which arise at anticrossings between spin energy levels. At CTs, the spin states are protected from magnetic noise and present an enhanced quantum coherence. Unfortunately, these optimal points are intrinsically hard to control since their transition energy cannot be tuned by an external magnetic field; moreover, their resilience towards geometric distortions has not yet been analyzed. Here we employ a python-based computational tool for the systematic theoretical analysis and chemical optimization of CTs. We compare three relevant case studies with increasingly complex ground states. First, we start with vanadium(iv)-based spin qubits, where the avoided crossings are controlled by hyperfine interaction and find that these S = 1/2 systems are very promising, in particular in the case of vanadyl complexes in an L-band pulsed EPR setup. Second, we proceed with a study of the effect of symmetry distortions in a holmium polyoxotungstate of formula [Ho(W₅O₁₈)₂]⁹⁻ where CTs had already been experimentally demonstrated. Here we determine the relative importance of the different structural distortions that causes the anticrossings. Third, we study the most complicated case, a polyoxopalladate cube [HoPd₁₂(AsPh)₈O₃₂]⁵⁻ which presents an unusually rich ground spin multiplet. This system allows us to find uniquely favorable CTs that could nevertheless be accessible with standard pulsed EPR equipment (X-band or Q-band) after a suitable chemical distortion to break the perfect cubic symmetry. Since anticrossings and CTs constitute a rich source of physical phenomena in very different kinds of quantum systems, the generalization of this study is expected to have impact not only in molecular spin science but also in other related fields such as molecular photophysics and photochemistry.

We employ a python computational tool to compare 3 relevant case studies with increasingly complex ground states: vanadyl complexes, Ho(iii) square antiprisms and Ho(iii) cubic structures.     

Spectrum of the molecular eigenstates of pyrazine

The molecular eigenstate spectrum belonging to the P and R branches of the¹B_3u(0-0) electronic transition of pyrazinc-h₄ was recorded with a 200 kHz wide laser in a supersome nozzle at a temperature of ≈ 1 K. The square of the former transform fo the amplitude spectrum yields the quantum beats in the fluorescence decay that have been reported before.     

Stark quantum beat spectroscopy: The vibrational dependence of the dipole moment in the A1Σ+ state of BaO

The method of quantum beat spectroscopy following pulsed dye laser excitation is applied to measure electric field splittings in excited states of the ¹³⁸Ba¹⁶O molecule. Stark quantum beats were observed in the fluorescent decay of the A¹Σ⁺ (ν′ = 0, 1, 2, 3, J′ = 1) states. From the observed beat frequencies values of electric dipole moments in different vibrational states were derived. The results are: μ(ν′ = 0) = 2.98(7) D, μ(ν′ = 1) = 2.66(7) D, μ(ν′ = 2)3.15(8) D and μ(ν′ = 3) = 3.18(8) D.     

Photon echoes in the 3P0 ← 3H4 transition of Pr3+/LaF3

Photon-echo quantum beats observed in the two-pulse and three-pulse photon echo of the ³P₀ ← ³H₄ transition in Pr³⁺/LaF₃ were used to determine the excited-state spin-hamiltonian. In addition we report on the anomalous stimulated photon echo observed in the same transition which in a magnetic field may acquire a lifetime of about 30 minutes.     

Lasing without inversion III: microwave coupling induced atomic coherence

We consider the nondegenerateA quantum beat laser, and investigate the possibility of lasing without population inversion when coherence is established, between the lower levels, by applying a strong microwave field. For a specific example we calculate how much coherence may be established between the lower levels using microwave coupling. Analytical calculations are presented for both the open and closed three level atomic systems, using perturbation theory up to third order in the optical fields. Taking the linear equations, we show numerically how gain may be achieved.