Nonlinear Optical Spectroscopy Research Articles

Plasmonic enhancement of third-order nonlinear optical susceptibilities in self-doped Cu_2-xS nanoparticles

Heavily doped Cu2-xS nanoparticles with hole densities of ~1021 cm−3 were chemically synthesized and their localized surface plasmon resonance (LSPR) in the near-infrared region was investigated by nonlinear optical spectroscopy. We found that their third-order susceptibility χ(3) exhibits resonant enhancement around LSPR, similar to that in plasmonic noble metal nanoparticles. It was found that the maximum χ(3) value of Cu2-xS nanoparticles was comparable to that of Au nanoparticles with the same dimensions and concentrations. Our results indicate that Cu2-xS nanoparticles can be used as nonlinear optical materials operating in the near-infrared region, even though their near-field enhancement effect is slightly weaker than that of Au nanoparticles.

Simultaneous generation of sub-5-femtosecond 400 nm and 800 nm pulses for attosecond extreme ultraviolet pump-probe spectroscopy.

Few-cycle laser pulses with wavelengths centered at 400 nm and 800 nm are simultaneously obtained through wavelength separation of ultrashort, spectrally broadened Vis-NIR laser pulses spanning 350-1100 nm wavelengths. The 400 nm and 800 nm pulses are separately compressed, yielding pulses with 4.4 fs and 3.8 fs duration, respectively. The pulse energy exceeds 5 μJ for the 400 nm pulses and 750 μJ for the 800 nm pulses. Intense 400 nm few-cycle pulses have a broad range of applications in nonlinear optical spectroscopy, which include the study of photochemical dynamics, semiconductors, and photovoltaic materials on few-femtosecond to attosecond time scales. The ultrashort 400 nm few-cycle pulses generated here not only extend the spectral range of the optical pulse for NIR-XUV attosecond pump-probe spectroscopy but also pave the way for two-color, three-pulse, multidimensional optical-XUV spectroscopy experiments.

Identifying diamagnetic interactions in scattering and nonlinear optics

In the generic formulation of optical interactions there is, beyond the familiar electric and magnetic multipolar forms of coupling, an additional diamagnetization term that rarely receives attention. In fact it can give rise to effects that should be observable in the general context of nonlinear optical spectroscopy, as well as scattering. A quantum electrodynamical analysis reveals features of special interest in two specific cases: two-photon absorption and Rayleigh scattering. Diamagnetic contributions are seen to be dispersion free with regards to the frequency of input radiation, and can represent unique interactions within optical absorption and emission processes. There is also a configuration in which diamagnetic couplings, which are quadratic in the magnetic field, can supersede those that are dependent linearly on the electric field strength, such as the electric dipole. In this connection the influence of retroreflected circularly polarized light, which leads to a local distance dependence in magnitude of the electromagnetic fields, produces conditions in which the diamagnetization response can become a prominent feature in two-photon absorption.

Communication: The origin of many-particle signals in nonlinear optical spectroscopy of non-interacting particles.

Nonlinear spectroscopy signals detected by fluorescence from dilute samples of N non-interacting molecules are usually adequately described by simply multiplying the single molecule response by N. We show that signals that scale with higher powers of N are generated by the joint detection of several particles. This can be accomplished by phase sensitive detection such as phase cycling, photo-acoustic modulation, or by Hanbury-Brown Twiss photon coincidence. Such measurements can dissect the ensemble according to the number of excited particles.

Ultrafast decoherence dynamics govern photocarrier generation efficiencies in polymer solar cells.

All-organic-based photovoltaic solar cells have attracted considerable attention because of their low-cost processing and short energy payback time. In such systems the primary dissociation of an optical excitation into a pair of photocarriers has been recently shown to be extremely rapid and efficient, but the physical reason for this remains unclear. Here, two-dimensional photocurrent excitation spectroscopy, a novel non-linear optical spectroscopy, is used to probe the ultrafast coherent decay of photoexcitations into charge-producing states in a polymer:fullerene based solar cell. The two-dimensional photocurrent spectra are interpreted by introducing a theoretical model for the description of the coupling of the electronic states of the system to an external environment and to the applied laser fields. The experimental data show no cross-peaks in the twodimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20 fs or less.

Simulation of optical response functions in molecular junctions.

We discuss theoretical approaches to nonlinear optical spectroscopy of molecular junctions. Optical response functions are derived in a form convenient for the implementation of Green function techniques, and their expressions in terms of pseudoparticle nonequilibrium Green functions are proposed. The formulation allows to account for both intramolecular interactions and hybridization of molecular states with those of contacts. Within a generic model and utilizing two-dimensional optical spectroscopy as an example, the methodology is compared with exact simulations and is shown to work where the traditional Liouville space approach fails.

Development and applications of nonlinear optical spectroscopy: 14th ECONOS/34th ECW meeting in Leuven (Belgium)

Development and applications of nonlinear optical spectroscopy: 14th ECONOS/34th ECW meeting in Leuven (Belgium)

Optical spectroscopy of molecular junctions: Nonequilibrium Green's functions perspective.

We consider optical spectroscopy of molecular junctions from the quantum transport perspective when radiation field is quantized and optical response of the system is simulated as photon flux. Using exact expressions for photon and electronic fluxes derived within the nonequilibrium Green function (NEGF) methodology and utilizing fourth order diagrammatic perturbation theory (PT) in molecular coupling to radiation field, we perform simulations employing realistic parameters. Results of the simulations are compared to the bare PT which is usually employed in studies on nonlinear optical spectroscopy to classify optical processes. We show that the bare PT violates conservation laws, while flux conserving NEGF formulation mixes optical processes.

The optimal antenna for nonlinear spectroscopy of weakly and strongly scattering nanoobjects

Optical nanoantennas, i.e., arrangements of plasmonic nanostructures, promise to enhance the light–matter interaction on the nanoscale. In particular, nonlinear optical spectroscopy of single nanoobjects would profit from such an antenna, as nonlinear optical effects are already weak for bulk material, and become almost undetectable for single nanoobjects. We investigate the design of optical nanoantennas for transient absorption spectroscopy in two different cases: the mechanical breathing mode of a metal nanodisk and the quantum-confined carrier dynamics in a single CdSe nanowire. In the latter case, an antenna with a resonance at the desired wavelength optimally increases the light intensity at the nanoobject. In the first case, the perturbation of the antenna by the investigated nanosystem cannot be neglected and off-resonant antennas become most efficient.

Optical Coherence in Atomic-Monolayer Transition-Metal Dichalcogenides Limited by Electron-Phonon Interactions

We systematically investigate the excitonic dephasing of three representative transition-metal dichalcogenides, namely, MoS_{2}, MoSe_{2}, and WSe_{2} atomic monolayer thick and bulk crystals, in order to gain a proper understanding of the factors that determine the optical coherence in these materials. Coherent nonlinear optical spectroscopy and temperature dependent absorption, combined with theoretical calculations of the phonon spectra, indicate electron-phonon interactions, to be the limiting factor. Surprisingly, the excitonic dephasing, differs only slightly between atomic monolayers and high quality bulk crystals, which indicates that material imperfections are not the limiting factor in atomically thin monolayer samples. The temperature dependence of the electronic band gap and the excitonic linewidth combined with "abinitio" calculations of the phonon energies and the phonon density of states reveal a strong interaction with the E' and E" phonon modes.

Stimulated Emission Enhancement Using Shaped Pulses.

Controlling stimulated emission is of importance because it competes with absorption and fluorescence under intense laser excitation. We performed resonant nonlinear optical spectroscopy measurements using femtosecond pulses shaped by π- or π/2-step phase functions and carried out calculations based on density matrix representation to elucidate the experimental results. In addition, we compared enhancements obtained when using other pulse shaping functions (chirp, third-order dispersion, and a time-delayed probe). The light transmitted through the high optical density solution was dominated by an intense stimulated emission feature that was 14 times greater for shaped pulses than for transform limited pulses. Coherent enhancement depending on the frequency, temporal, and phase characteristics of the shaped pulse is responsible for the experimental observations.

Linear and Nonlinear Optical Spectroscopy of Fluoroalkylated BODIPY Dyes

A series of fluoroalkyl-labeled BODIPY dyes have been synthesized with different substituents on the 2- and 6-positions and investigated in terms of their spectroscopic properties. The dyes were decorated with aryl, alkenyl, and alkynyl substituents, respectively. Those substituents are able to expend the dyes’ delocalized π-electron system to different extents. Detailed linear and nonlinear optical spectroscopy methods as well as quantum-chemical calculations have been employed to verify the influence of those different substituents on the electronic distribution and, ultimately, on the molecules’ optical properties. From the nonlinear optical measurements, we find that the substituents highly influence the excited-state absorption properties, which could be tuned in wavelength by ∼100 nm and in magnitude by over 1 order of magnitude, reaching peak values close to 10–15 cm2 for one of the alkynyl-containing dyes.

Globalk-space analysis of electron-phonon interaction in graphene and application toM-point spectroscopy

Recently, optical probes have become available that can access and observe energy renormalization due to electron-phonon interaction in graphene away from the well-studied Dirac $K$ point. Using an expanded deformation potential approach, we present a theoretical study of the electron-phonon self-energy and scattering matrix elements across the entire Brillouin zone. We elucidate the roles of modulated hopping and conventional deformation potential coupling, parameterized via standard deformation potentials, the in-plane phonon modes, intra- and interband contributions, and umklapp processes. Applying the theory to nonlinear optical transmission spectroscopy in the vicinity of the $M$ point, we find very good agreement with recently published experimental data.

Laboratory Studies of Nonlinear Optical Signals for Caries Detection

Multiphoton confocal microscopy and nonlinear spectroscopy are used to investigate the caries process in dentin. Although dentin is a major calcified tissue of the teeth, its organic phase comprises type I collagen fibers. Caries drive dentin demineralization and collagen denaturation. Multiphoton microscopy is a powerful imaging technique: the biological materials are transparent to infrared frequencies and can be excited to penetration depths inaccessible to 1-photon confocal microscopy. The laser excitation greatly reduces photodamage to the sole focal region, and the signal-to-noise ratio is improved significantly. The method has been used to follow pathologic processes involving collagen fibrosis or collagen destruction based on their 2-photon excited fluorescence (2PEF) emission and second harmonic generation (SHG). Combining multiphoton imaging with nonlinear spectroscopy, we demonstrate that both 2PEF and SHG intensity of human dentin are strongly modified during the tooth caries process, and we show that the ratio between SHG and 2PEF signals is a reliable parameter to follow dental caries. The ratio of the SHG/2PEF signals measured by nonlinear optical spectroscopy provides valuable information on the caries process, specifically on the degradation of the organic matrix of dentin. The goal is to bring these nonlinear optical signals to clinical application for caries diagnosis.

Imaging and Modelling Tissue Structure to Inform the Development of Musculoskeletal Therapies

Biomanufacturing is moving rapidly towards recreating the complex, hierarchical structures of native tissues. With such advances comes a need to provide a detailed characterisation of the physical interaction between synthetic structures and the biological environment, and to provide increasingly detailed and/or specific targets for synthesis/manufacturing. The musculoskeletal system is a functionally challenging environment in which to apply these synthetic constructs, reflected in the difficulties faced by current treatment approaches. Limited information on the functional role of low-level structural features provides a further challenge. Here, we discuss imaging and modelling approaches for providing this characterisation, focusing on scanning probe microscopy, nonlinear optical methods and vibrational spectroscopy for probing structure, and numerical modeling to explore the potential roles of observed structural features.

Advances in nonlinear optical spectroscopies: a historical perspective of developments and applications presented at ECONOS

This article reviews the contributions to the special issues of the annual European Conference on Nonlinear Optical Spectroscopy (ECONOS) since its establishment in 2002. The review does not only highlight the developments of the scientific areas related to nonlinear optical spectroscopy in Europe but also shows how different sub‐fields evolved globally because ECONOS evolved as an international meeting attracting participants from all over the world. Four main topical categories are identified: (1) theoretical and instrumental developments, (2) applications to gas‐phase and combustion systems, (3) applications to condensed phase matter, and (4) development and applications of micro‐spectroscopy methods. Copyright © 2015 John Wiley & Sons, Ltd.

Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table.

In this report, we summarize and describe the recent unique updates and additions to the Molcas quantum chemistry program suite as contained in release version 8. These updates include natural and spin orbitals for studies of magnetic properties, local and linear scaling methods for the Douglas-Kroll-Hess transformation, the generalized active space concept in MCSCF methods, a combination of multiconfigurational wave functions with density functional theory in the MC-PDFT method, additional methods for computation of magnetic properties, methods for diabatization, analytical gradients of state average complete active space SCF in association with density fitting, methods for constrained fragment optimization, large-scale parallel multireference configuration interaction including analytic gradients via the interface to the Columbus package, and approximations of the CASPT2 method to be used for computations of large systems. In addition, the report includes the description of a computational machinery for nonlinear optical spectroscopy through an interface to the QM/MM package Cobramm. Further, a module to run molecular dynamics simulations is added, two surface hopping algorithms are included to enable nonadiabatic calculations, and the DQ method for diabatization is added. Finally, we report on the subject of improvements with respects to alternative file options and parallelization.

Exciton states in monolayer MoSe2: impact on interband transitions

We combine linear and nonlinear optical spectroscopy at 4 K with ab initio calculations to study the electronic bandstructure of MoSe2 monolayers. In one-photon photoluminescence excitation (PLE) and reflectivity we measure a separation between the A- and B-exciton emission of 220 meV, in good agreement with our calculations. In two-photon PLE we detect for the A- and B-exciton the 2p state 180 meV above the respective 1s state. In second harmonic generation (SHG) spectroscopy we record an enhancement by more than two orders of magnitude of the SHG signal at resonances of the charged exciton and the 1s and 2p neutral A- and B-exciton. Our post-density functional theory calculations show in the conduction band along the K–Γ direction a local minimum at the Λ-point that is energetically and in k-space close to the global minimum at the K-point. The influence of this local minimum on exciton transitions is discussed.

Linear and Nonlinear Optical Spectroscopy at the Nanoscale with Photoinduced Force Microscopy.

The enormous advances made in nanotechnology have also intensified the need for tools that can characterize newly synthesized nanoaterials with high sensitivity and with high spatial resolution. Many existing tools with nanoscopic resolution or better, including scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) methods, can generate highly detailed maps of nanoscopic structures. However, while these approaches provide great views of the morphological properties of nanomaterials, it has proven more challenging to derive chemical information from the corresponding images. To address this issue, attempts have been made to dress existing nanoscopy methods with spectroscopic sensitivity. A powerful approach in this direction is the combination of scan probe techniques with optical illumination, which aims to marry the nanoscopic resolution provided by a sharp tip with the chemical selectivity provided by optical spectroscopy. Examples of this approach include existing techniques such as scattering-type scanning near-field optical microscopy and tip-enhanced Raman spectroscopy. A new and emerging technique in this direction is photoinduced force microscopy (PiFM), which enables spectroscopic probing of materials with a spatial resolution well under 10 nm. In PiFM, the sample is optically excited and the response of the material is probed directly in the near-field by reading out the time-integrated force between the tip and the sample. Because the magnitude of the force is dependent on the photoinduced polarization in the sample, PiFM exhibits spectroscopic sensitivity. The photoinduced forces measured in PiFM are spatially confined on the nanometer scale, which translates into a very high spatial resolution even under ambient conditions. The PiFM approach is compatible with a wide range optical excitation frequencies, from the visible to the mid-infrared, enabling nanoscale imaging contrast based on either electronic or vibrational transitions in the sample. These properties make PiFM an attractive method for the visualization and spectroscopic characterization of a vast variety of nano materials, from semiconducting nanoparticles to polymer thin films to sensitive measurements of single molecules. In this Account, we review the principles of the PiFM technique and discuss the basic components of the photoinduced force microscope. We highlight the imaging properties of the PiFM instrument and demonstrate the inherent spectroscopic sensitivity of the technique. Furthermore, we show that the PiFM approach can be used to probe both the linear and nonlinear optical properties of nano materials. In addition, we provide several examples of PiFM imaging applications.

Development and applications of nonlinear optical spectroscopy: 13th ECONOS/33rd ECW meeting in Dole (France)

Development and applications of nonlinear optical spectroscopy: 13th ECONOS/33rd ECW meeting in Dole (France)