Marten Richter

Tunable Plasmon Coupling in Distance-Controlled Gold Nanoparticles

Plasmons are resonant excitations in metallic films and nanoparticles. For small enough static distances of metal nanoparticles, additional plasmon-coupled modes appear as a collective excitation between the nanoparticles. Here we show, by combining poly(N-isopropylacrylamide) micro- and nanospheres and Au nanoparticles, how to design a system that allows controllably and reversibly switching on and off, and tuning the plasmon-coupled mode.

Novel Au−Ag Hybrid Device for Electrochemical SE(R)R Spectroscopy in a Wide Potential and Spectral Range

A nanostructured gold-silver-hybrid electrode for SER spectroelectrochemistry was developed which advantageously combines the electrochemical properties and chemical stability of Au and the strong surface enhancement of (resonance) Raman scattering by Ag. The layered device consists of a massive nanoscopically rough Ag electrode, a thin (2 nm) organic layer, and a ca. 20 nm thick Au film that may be coated by self-assembled monolayers for protein adsorption. The SERR-spectroscopic and electrochemical performance of this device is demonstrated using the heme protein cytochrome c as a benchmark model system, thereby extending, for the first time, SE(R)R studies of molecules on Au surfaces to excitation in the violet spectral range. The enhancement factor is only slightly lower than for Ag electrodes which can be rationalized in terms of an efficient transfer of plasmon resonance excitation from the Ag to the Au coating. This mechanism, which requires a thin dielectric layer between the two metals, is supported by theoretical calculations.

Trion formation dynamics in monolayer transition metal dichalcogenides

We report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides, specifically molybdenum diselenide (MoSe2), using resonant two-color pump-probe spectroscopy. When resonantly pumping the exciton transition, trions are generated on a picosecond time scale through exciton-electron interaction. As the pump energy is tuned from the high energy to low energy side of the inhomogeneously broadened exciton resonance, the trion formation time increases by ∼50%. This feature can be explained by the existence of both localized and delocalized excitons in a disordered potential and suggests the existence of an exciton mobility edge in transition metal dichalcogenides.

Two-Dimensional Double-Quantum Spectra Reveal Collective Resonances in an Atomic Vapor

We report the observation of double-quantum coherence signals in a gas of potassium atoms at twice the frequency of the one-quantum coherences. Since a single atom does not have a state at the corresponding energy, this observation must be attributed to a collective resonance involving multiple atoms. These resonances are induced by weak interatomic dipole-dipole interactions, which means that the atoms cannot be treated in isolation, even at a low density of 10(12)  cm(-3).

Neutral and Charged Inter-Valley Biexcitons in Monolayer MoSe2

In atomically thin transition metal dichalcogenides (TMDs), reduced dielectric screening of the Coulomb interaction leads to strongly correlated many-body states, including excitons and trions, that dominate the optical properties. Higher-order states, such as bound biexcitons, are possible but are difficult to identify unambiguously using linear optical spectroscopy methods. Here, we implement polarization-resolved two-dimensional coherent spectroscopy (2DCS) to unravel the complex optical response of monolayer MoSe2 and identify multiple higher-order correlated states. Decisive signatures of neutral and charged inter-valley biexcitons appear in cross-polarized two-dimensional spectra as distinct resonances with respective ∼20 and ∼5 meV binding energies—similar to recent calculations using variational and Monte Carlo methods. A theoretical model considering the valley-dependent optical selection rules reveals the quantum pathways that give rise to these states. Inter-valley biexcitons identified here, comprising of neutral and charged excitons from different valleys, offer new opportunities for developing ultrathin biexciton lasers and polarization-entangled photon sources.

Few-photon model of the optical emission of semiconductor quantum dots.

The Jaynes-Cummings model provides a well established theoretical framework for single electron two level systems in a radiation field. Similar exactly solvable models for semiconductor light emitters such as quantum dots dominated by many particle interactions are not known. We access these systems by a generalized cluster expansion, the photon-probability cluster expansion: a reliable approach for few-photon dynamics in many body electron systems. As a first application, we discuss vacuum Rabi oscillations and show that their amplitude determines the number of electrons in the quantum dot.

Numerically exact solution of the many emitter–cavity laser problem: Application to the fully quantized spaser emission

A numerically exact solution to the many emitter -- cavity problem as an open many body system is presented. The solution gives access to the full, nonperturbative density matrix and thus the full quantum statistics and quantum correlations. The numerical effort scales with the third power in the number of emitters. Notably the solution requires none of the common approximations like good/bad cavity limit. As a first application the recently discussed concept of coherent surface plasmon amplification -- spaser -- is addressed: A spaser consists of a plasmonic nanostructure that is driven by a set of quantum emitters. In the context of laser theory it is a laser in the (very) bad cavity limit with an extremely high light matter interaction strength. The method allows us to answer the question of spasing with a fully quantized theory.

Optically Excited Entangled States in Organic Molecules Illuminate the Dark.

We utilize quantum entangled photons to carry out nonlinear optical spectroscopy in organic molecules with an extremely small number of photons. For the first time, fluorescence is reported as a result of entangled photon absorption in organic nonlinear optical molecules. Selectivity of the entangled photon absorption process is also observed and a theoretical model of this process is provided. Through these experiments and theoretical modeling it is found that while some molecules may not have strong classical nonlinear optical properties due to their excitation pathways; these same excitation pathways may enhance the entangled photon processes. It is found that the opposite is also true. Some materials with weak classical nonlinear optical effects may exhibit strong non-classical nonlinear optical effects. Our entangled photon fluorescence results provide the first steps in realizing and demonstrating the viability of entangled two-photon microscopy, remote sensing, and optical communications.

A Bloch equation approach to intensity dependent optical spectra of light harvesting complex II

On the basis of the recent progress in the resolution of the structure of the antenna light harvesting complex II (LHC II) of the photosystem II, we propose a microscopically motivated theory to predict excitation intensity-dependent spectra. We show that optical Bloch equations provide the means to include all 2N excited states of an oligomer complex of N coupled two-level systems and analyze the effects of Pauli Blocking and exciton–exciton annihilation on pump-probe spectra. We use LHC Bloch equations for 14 Coulomb coupled two-level systems, which describe the S0 and S1 level of every chlorophyll molecule. All parameter introduced into the Hamiltonian are based on microscopic structure and a quantum chemical model. The derived Bloch equations describe not only linear absorption but also the intensity dependence of optical spectra in a regime where the interplay of Pauli Blocking effects as well as exciton–exciton annihilation effects are important. As an example, pump-probe spectra are discussed. The observed saturation of the spectra for high intensities can be viewed as a relaxation channel blockade on short time scales due to Pauli blocking. The theoretical investigation is useful for the interpretation of the experimental data, if the experimental conditions exceed the low intensity pump limit and effects like strong Pauli Blocking and exciton–exciton annihilation need to be considered. These effects become important when multiple excitations are generated by the pump pulse in the complex.

Nonperturbative theory for the optical response to strong light of the light harvesting complex II of plants: saturation of the fluorescence quantum yield.

Recent progress in resolution of the structure of the light harvesting complex II provides the basis for theoretical predictions on nonlinear optical properties from microscopic calculations. An approach to absorption and fluorescence is presented within the framework of Bloch equations using a correlation expansion of relevant many particle interactions. The equations derived within the framework of this theory are applied to describe fluorescence saturation phenomena. The experimentally observed decrease of the normalized fluorescence quantum yield from 1 to 0.0001 upon increasing the intensity of laser pulse excitation at 645 nm by five orders of magnitude [R Schödel et al., Biophys. J. 71, 3370 (1996)] is explained by Pauli blocking effects of optical excitation and excitation energy transfer.