Accumulation effects in modulation spectroscopy with high repetition rate pulses: recursive solution of optical Bloch equations

Application of the phase modulated pulsed light for advance spectroscopic measurements is the area of growing interest. The phase modulation of the light causes modulation of the signal. Separation of the spectral components of the modulations allows to distinguish the contributions of various interaction pathways. The lasers with high repetition rate used in such experiments can lead to appearance of the accumulation effects, which become especially pronounced in systems with long-living excited states. Recently it was shown, that such accumulation effects can be used to evaluate parameters of the dynamical processes in the material. In this work we demonstrate that the accumulation effects are also important in the quantum characteristics measurements provided by modulation spectroscopy. In particular, we consider a model of quantum two-level system driven by a train of phase-modulated light pulses, organised in analogy with the 2D spectroscopy experiments. We evaluate the harmonics' amplitudes in the fluorescent signal and calculate corrections appearing from the accumulation effects. We show that the corrections can be significant and have to be taken into account at analysis of experimental data.Comment: 10 pages, 5 figure

Exciton coupling induces vibronic hyperchromism in light-harvesting complexes

The recently suggested possibility that weak vibronic transitions can be excitonically enhanced in light-harvesting complexes is studied in detail. A vibronic exciton dimer model which includes ground state vibrations is investigated using multi-configuration time-dependent Hartree method with a parameter set typical to photosynthetic light-harvesting complexes. Absorption spectra are discussed in dependence on the Coulomb coupling, the detuning of site energies, and the number of vibrational mode. Calculations of the fluorescence spectra show that the spectral densities obtained from the low temperature fluorescence line narrowing measurements of light-harvesting systems need to be corrected for the exciton effects. For the J-aggregate configuration, as in most of the light-harvesting complexes, the true spectral density has larger amplitude than what is obtained from the measurement.Comment: revised version (minor

Classification of Dark States in Multi-level Dissipative Systems

Dark states are eigenstates or steady-states of a system that are decoupled from the radiation. Their use, along with associated techniques such as Stimulated Raman Adiabatic Passage, has extended from atomic physics where it is an essential cooling mechanism, to more recent versions in condensed phase where it can increase the coherence times of qubits. These states are often discussed in the context of unitary evolution and found with elegant methods exploiting symmetries, or via the Bruce-Shore transformation. However, the link with dissipative systems is not always transparent, and distinctions between classes of CPT are not always clear. We present a detailed overview of the arguments to find stationary dark states in dissipative systems, and examine their dependence on the Hamiltonian parameters, their multiplicity and purity. We find a class of dark states that depends not only on the detunings of the lasers but also on their relative intensities. We illustrate the criteria with the more complex physical system of the hyperfine transitions of $^{87}$Rb and show how a knowledge of the dark state manifold can inform the preparation of pure states.Comment: additional example

Optimization Schemes for Efficient Multiple Exciton Generation and Extraction in Colloidal Quantum Dots

Multiple exciton generation is a process in which more than one electron hole pair is generated per absorbed photon. It allows us to increase the efficiency of solar energy harvesting. Experimental studies have shown the multiple exciton generation yield of 1.2 in isolated colloidal quantum dots. However real photoelectric devices require the extraction of electron hole pairs to electric contacts. We provide a systematic study of the corresponding quantum coherent processes including extraction and injection and show that a proper design of extraction and injection rates enhances the yield significantly up to values around 1.6.Comment: 5 pages, accepted by The Journal of Chemical Physic

The nature of relaxation processes revealed by the action signals of phase modulated light fields

We introduce a generalized theoretical approach to study action signals induced by the absorption of two-photons from two phase modulated laser beams and subject it to experimental testing for two types of photoactive samples, solution of rhodamine 6G and GaP photodiode. In our experiment, the phases of the laser beams are modulated at the frequencies f1 and f2, respectively. The action signals, such as photoluminescence and photocurrent, which result from the absorption of two photons, are isolated at frequencies m f (f=|f1-f2|, m=0,1,2...). We demonstrate that the ratio of the amplitudes of the secondary (m=2) and the primary (m=1) signals is sensitive to the type of relaxation process taken place in the system and thus can be used for its identification. Such sensitivity originates from cumulative effects of non-equilibrated state of the system between the light pulses. When the cumulative effects are small, i.e. the relaxation time is much shorter then the laser repetition rate or the laser intensity is high enough to dominate the system behavior, the ratio achieves its reference value 1:4 (the signature of two-photon absorption). In the intermediate regimes the ratio changes rapidly with the growth of intensity from zero value in case of second order relaxation process, while it demonstrates slow monotonic decrease for linear relaxation. In the article we also determine the value of the recombination rate in a GaP photodiode by using the above approach

Digital Cavities and Their Potential Applications

The concept of a digital cavity is presented. The functionality of a tunable radio-frequency/microwave cavity with unrestricted Q-factor is implemented. The theoretical aspects of the cavity and its potential applications in high resolution spectroscopy and synchronization of clocks together with examples in signal processing and data acquisition are discussed

Generalized lock-in amplifier for precision measurement of high frequency signals

We herein formulate the concept of a generalized lock-in amplifier for the precision measurement of high frequency signals based on digital cavities. Accurate measurement of signals higher than 200 MHz using the generalized lock-in is demonstrated. The technique is compared with a traditional lock-in and its advantages and limitations are discussed. We also briefly point out how the generalized lock-in can be used for precision measurement of giga-hertz signals by using parallel processing of the digitized signals

Using Fluorescence Detected Two-Dimensional Spectroscopy to Investigate Initial Exciton Delocalization Between Coupled Chromophores

F\"orster theory describes electronic exciton energy migration in molecular assemblies as an incoherent hopping process between donor and acceptor molecules. The rate is expressed in terms of the overlap integral between donor fluorescence and acceptor absorption spectra. Typical time scales for systems like photosynthetic antennae are on the order of a few picoseconds. Prior to transfer it is assumed that the initially excited donor molecule has equilibrated with respect to the local environment. However, upon excitation and during the equilibration phase the state of the system needs to be described by the full density matrix, including coherences between donor and acceptor states. While being intuitively clear, addressing this regime experimentally has been a challenge until the recently reported advances in Fluorescence Detected Two-Dimensional Spectroscopy (FD2DS). Here, we demonstrate using fourth order perturbation theory, the conditions for the presence of donor-acceptor coherence induced cross-peaks at zero waiting time between the first and the second pair of pulses. The approach is illustrated for a heterodimer model which facilitates an analytical solution.Comment: corrected versio