Nonlinear Spectroscopy Research Articles

Ultrasensitive Detection and Separation of Pancreatic Cancer Biomarker CA 19-9 Using a Multiphoton Laser Wave-Mixing Detector Interfaced to Capillary Electrophoresis.

The carbohydrate antigen 19-9 (CA 19-9) is the most commonly used biomarker in the clinical diagnosis of pancreatic cancer. Multiphoton nonlinear laser wave-mixing spectroscopy is presented as an ultrasensitive detection method for CA 19-9. Wave mixing is an optical absorption-based method, and hence, one can detect CA 19-9 without labels in their native form using compact ultraviolet (UV) lasers or labeled samples using a visible laser. The wave-mixing signal exhibits a quadratic dependence on the sample concentration, and hence, it is an ideal sensor to monitor small changes in the sample. Wave mixing has inherent advantages over other absorption-based detection methods, including short optical path length (micrometer-thin samples instead of 1 cm cuvette) and excellent spatial resolution (micrometer probe). Since the laser wave-mixing probe volume is small (picoliter), it is convenient to interface to microfluidics or capillary-based electrophoresis systems to enhance chemical specificity. Our wave-mixing detectors could be configured as portable battery-powered devices suitable for field use. Laser wave-mixing spectroscopy offers enhanced selectivity levels for protein detection when coupled with capillary electrophoresis (CE). We report a concentration detection limit of 0.16 U/mL, and a corresponding mass detection limit of 1.2 × 10-8 U, and these detection limits are better than those of chemiluminescence- or ELISA- based methods.

Double-quantum spectroscopy of dense atomic vapors: Interplay between Doppler and self-broadenings.

In this article, we present a simulation study of the linear and nonlinear spectroscopy of dense atomic vapors. Motivated by recent experiments, we focus on double quantum spectroscopy, which directly probes dipole-dipole interactions. By explicitly including thermal velocity, we show that temperature has an important impact on the self-broadening mechanisms of the linear and nonlinear spectra. We also provide analytical expressions for the response functions in the short time limit using the two-body approximation, which shows that double quantum spectroscopy for atomic vapors directly probes the transition amplitude of the electronic excitation between two atoms. We also propose an expression for the double quantum spectrum that includes the effect of Doppler broadening, and we discuss the effect of density on the spectrum. We show that when Doppler broadening is negligible compared to self-broadening, the double quantum spectrum scales with the atomic density, while when Doppler broadening dominates, it scales as the square of the density.

Slow solvation dynamics beyond dielectric relaxation by three-pulse photon echo peak shift.

The dynamics of a liquid and its coupling to a solute are crucial for a better understanding of chemical processes in the liquid phase. In isotropic and homogeneous solutions, the time-correlation function of a solute is expected to vanish over time due to the translational and diffusive motions of the solvent. The three-pulse photon echo peak shift (3PEPS) is a third-order nonlinear spectroscopy technique that records the time-correlation function of a solute molecule in a solution, including an offset (inhomogeneity). In this work, we utilized a diffractive optics-based 3PEPS apparatus to fully resolve the dynamics in liquids from femtoseconds to nanoseconds while varying the temperature in the range of 80-298K and the probe solute molecules. Our observations reveal dynamics slower than the dielectric relaxation of n-alcohols, even at room temperature, consisting of a ∼0.5ns time constant that persists below the melting points and a static component (offset) on a nanosecond timescale. Based on the experiments, we suggest that locally formed glass-like clusters in liquids can be responsible for the slow dynamics. Our results may provide new insights into the dynamics of liquids and related phenomena such as liquid-glass and liquid-liquid phase transitions.

Spectroscopic Identification of the Charge Transfer State in Thiophene/Fullerene Heterojunctions: Electroabsorption Spectroscopy from GW/BSE Calculations.

Creation of charge transfer (CT) states in bulk heterojunction systems such as C60/polymer blends is an important intermediate step in the creation of carriers in organic photovoltaic systems. CT states generally have small oscillator strengths in linear optical absorption spectroscopy owing to limited spatial overlap of electron and hole wave functions in the CT excited state. Electroabsorption spectroscopy (EA) exploits changes in wave function character of CT states in response to static electric fields to enhance detection of CT states via nonlinear optical absorption spectroscopies. A 4 × 4 model Hamiltonian is used to derive splittings of even and odd Frenkel (FR) excited states and changes in wave function character of CT excited states in an external electric field. These are used to explain why FR and CT states yield EA lineshapes which are first and second derivatives of the linear optical absorption spectrum. The model is applied to ammonia-borane molecules and pairs of molecules with large and small B-N separations and CT or FR excited states. EA spectra are obtained from differences in linear optical absorption spectra in the presence or absence of a static electric field and from perturbative sum over states (SOS) configuration interaction singles χ(2) and χ(3) nonlinear susceptibility calculations. Good agreement is found between finite field (FF) and SOS methods at field strengths similar to those used in EA experiments. EA spectra of three C60/oligothiophene complexes are calculated using the SOS method combined with GW/BSE methods. For these C60/oligothiophene complexes, we find several CT states in a narrow energy range in which charge transfer from the thiophene HOMO level to several closely spaced C60 acceptor levels yields an EA signal around 10% of the signal from oligothiophene.

Metasurface for broadband coherent Raman signal enhancement beyond the single-molecule detection threshold

Broadband enhancement of Raman signals is vital for molecular spectroscopy and sensing applications. However, typically, there is a compromise between the resonance width and the local field enhancement factors. Here, we merge the broadband open plasmonic cavity concepts with the geometry exploiting narrow gaps and a reflecting layer. This results in a metasurface design that maintains substantial electric field confinement in the gap volume accompanied by a broad spectral response. The confined field is enhanced through constructive interference between the plasmonically enhanced illuminating beam and the field reflected at the bottom layer. The resulting field can interact with analyte molecules and support Raman scattering. With an optimized metasurface geometry involving a pair of gold nanodisks and a thin gold film, we demonstrate numerically that our metasurface can simultaneously enhance Raman signals from various molecular species, potentially resulting in unprecedented signal intensities enhanced by up to 20 orders of magnitude, facilitating molecular detection and identification. Our design offers a practical and promising solution for improving the sensitivity of Raman techniques and has significant implications for the field of nonlinear optical spectroscopy. Moreover, our metasurface is compatible with current fabrication technologies, making it suitable for various applications in sensing and imaging.

Mitigating self-desiccation of cement composites via cellulose microfibers: Evidence of the microscopic behavior

Water-saturated cellulose microfibers (CMFs) incorporated into fresh cement composites can mitigate microcracking induced by self-desiccation during drying. This study utilized a nonlinear impact resonance acoustic spectroscopy (NIRAS) technique to elucidate the mechanism underlying the CMF-driven mitigation of self-desiccation. The hysteresis nonlinearity parameter (α) from the NIRAS was used to quantify the microstructural changes in three different mixtures (0 0.3 and 1% dosages of CMFs). Computed tomography (CT) compression tests and periodic measurements of mass and resonance frequency were performed to obtain more insights into mitigating self-desiccation. Supported by the collected data the results show a remarkable reduction in α over time confirming high sensitivity of α to the microstructural change. Furthermore the trend of α was consistent with the pore size distribution estimated by the CT test which provides quantitative evidence to support the mitigation of self-desiccation promoted by CMFs. We envision that these findings can be used as guidelines for enhancing the durability of cement composites facilitated by CMFs.

Detecting driving potentials at the buried SiO2 nanolayers in solar cells by chemical-selective nonlinear x-ray spectroscopy

We present an approach to selectively examine an asymmetric potential in the buried layer of solar cell devices by means of nonlinear x-ray spectroscopy. Detecting second harmonic generation signals while resonant to the SiO2 core level, we directly observe existence of the band bending effect in the SiO2 nanolayer, buried in the heterostructures of Al/LiF/SiO2/Si, TiO2/SiO2/Si, and Al2O3/SiO2/Si. The results demonstrate high sensitivity of the method to the asymmetric potential that determines performance of functional materials for photovoltaics or other optoelectronic devices.

Recognition of bovine hemoglobin protein on molecularly imprinted polymer surfaces using nonlinear vibrational spectroscopy

Advancement in molecularly imprinted biomimetics has aided in developing robust artificial recognition-based materials, which can be customized for bio/chemo-sensing of distinct molecules. The present study reports a simple one-step synthesis and analysis of protein-imprinted polymer thin films as a recognition element directly onto a solid support. Dopamine has been explored as a versatile functional monomer for a molecularly imprinted polymer (MIP) matrix to fabricate polydopamine (PDA) thin films with bovine hemoglobin as a template protein molecule. A detailed molecular-level insight into the recognition of the template molecule at each step has been investigated using vibrational sum frequency generation (VSFG) spectroscopy. A suitable PDA-coated thin film is selected based on the extent of polymerized intermediates formed after non-imprinted polymer fabrication at different time durations. An optimally prepared film of MIP is specified by observing the spectral signature of the methyl groups from protein molecules at the air–polymer interface. The template removal from MIP films after the washing procedure and subsequent re-binding of the protein molecules were evaluated by VSFG spectroscopy. The insightful molecular-level findings from SFG spectroscopy demonstrate the fabrication of an imprinted matrix as a label-free chemical sensor.

Phonon Polaritonics in Broad Terahertz Frequency Range with Quantum Paraelectric SrTiO3.

Photonics in the frequency range of 5-15terahertz (THz) potentially open a new realm of quantum materials manipulation and biosensing. This range, sometimes called "the new terahertz gap", is traditionally difficult to access due to prevalent phonon absorption bands in solids. Low-loss phonon-polariton materials may realize sub-wavelength, on-chip photonic devices, but typically operate in mid-infrared frequencies with narrow bandwidths and are difficult to manufacture on a large scale. Here, for the first time, quantum paraelectric SrTiO3 enables broadband surface phonon-polaritonic devices in 7-13THz. As a proof of concept, polarization-independent field concentrators are designed and fabricated to locally enhance intense, multicycle THz pulses by a factor of 6 and increase the spectral intensity by over 90 times. The time-resolved electric field inside the concentrators is experimentally measured by THz-field-induced second harmonic generation. Illuminated by a table-top light source, the average field reaches 0.5GVm-1 over a large volume resolvable by far-field optics. Theseresults potentially enable scalable THz photonics with high breakdown fields made of various commercially available phonon-polariton crystals for studying driven phases in quantum materials and nonlinear molecular spectroscopy.

Electro-Optic Sampling of a Free-Running Terahertz Quantum-Cascade-Laser Frequency Comb

Quantum-cascade-laser (QCL) frequency combs are compact semiconductor light sources operating in the mid-IR and terahertz frequencies. Achieving subpicosecond laser pulses with high peak power is of vital importance for performing nonlinear time-resolved spectroscopy as well for exploring nonlinear phenomena. Therefore, investigation and characterization of time-resolved free-running laser emission is a key for further improvement and optimization of these intersubband devices. In this work, we demonstrate a direct electric field measurement of a free-running terahertz QCL frequency comb using electro-optic sampling in combination with computational phase correction, where we retrieve the electric field profile and access the comb parameters. The demonstrated method is of high interest for time-resolved low-power laser emission characterization, typical for ring terahertz QCL frequency combs and investigation of phase-compensated emission via waveguide dispersion engineering for broadband comb operation.

Spatially Resolved Nonlinear Plasmonics.

Nonlinear optical plasmonics investigates the emission of plasmonic nanoantennas with the aid of nonlinear spectroscopy. Here we introduce nonlinear spatially resolved spectroscopy (NSRS) which is capable of imaging the k-space as well as spatially resolving the THG signal of gold nanoantennas and investigating the emission of individual antennas by wide-field illumination of entire arrays. Hand in hand with theoretical simulations, we demonstrate our ability of imaging various oscillation modes inside the nanostructures and therefore spatial emission hotspots. Upon increasing intensity of the femtosecond excitation, an individual destruction threshold can be observed. We find certain antennas becoming exceptionally bright. By investigating those samples taking structural SEM images of the nanoantenna arrays afterward, our spatially resolved nonlinear image can be correlated with this data proving that antennas had deformed into a peanut-like shape. Thus, our NSRS setup enables the investigation of a nonlinear self-enhancement process of nanoantennas under critical laser excitation.

Extracting spinon self-energies from two-dimensional coherent spectroscopy

Two-dimensional coherent spectroscopy (2DCS) is a nonlinear spectroscopy technique capable of identifying whether apparent continua in linear response are made out of multiplets of sharp deconfined quasiparticles. This makes it a potent tool for experimental identification of fractionalized phases. Previous discussions have focused on limits where the quasiparticles in question are infinitely long lived. In this paper we discuss 2DCS in the regime where the fractionalized quasiparticles can themselves decay. We introduce a powerful path-integral-based approach, whereby the computation of nonlinear susceptibilities reduces to an efficient exercise in diagrammatic perturbation theory. We apply this method to compute the 2DCS response of the one-dimensional transverse field Ising model, in the presence of integrability-breaking perturbations. We discuss aspects of the self-energy of the fractionalized quasiparticles that may be extracted via 2DCS, such as the momentum-dependent decay rate.

Two-dimensional coherent spectroscopy of trion-polaritons and exciton-polaritons in atomically thin transition metal dichalcogenides

We present a microscopic many-body calculation of the nonlinear two-dimensional coherent spectroscopy (2DCS) of trion-polaritons and exciton-polaritons in charge-tunable transition-metal-dichalcogenides monolayers placed in an optical microcavity. The charge tunability leads to an electron gas with nonzero density that brings brightness to the trion — a polaron quasiparticle formed by an exciton with a nonzero residue bounded to the electron gas. As a result, a trion-polariton is created under strong light-matter coupling, as observed in the recent experiment by Sidler et al. [Nat. Phys. 13, 255 (2017)]. We analyze in detail the structure of trion-polaritons, by solving an extended Chevy ansatz for the trion quasiparticle wave-function. We confirm that the effective light-matter coupling for trion-polaritons is determined by the residue of the trion quasiparticle. The solution of the full many-body polaron states within Chevy ansatz enables us to microscopically calculate the nonlinear 2DCS spectrum of both trion-polaritons and exciton-polaritons. We predict the existence of three kinds of off-diagonal cross-peaks in the 2DCS spectrum, as an indication of the coherence among the different branches of trion-polaritons and exciton-polaritons. Due to the sensitivity of 2DCS spectrum to quasiparticle interactions, our work provides a good starting point to explore the strong nonlinearity exhibited by trion-polaritons in some recent exciton-polariton experiments.

Adsorption of SARS-CoV-2 Spike (N501Y) RBD to Human Angiotensin-Converting Enzyme 2 at a Lipid/Water Interface.

The receptor binding domain (RBD) of spike proteins plays a crucial role in the process of severe acute respiratory syndrome corona virus 2 (SARS-CoV-2) attachment to the human angiotensin-converting enzyme 2 (ACE2). The N501Y mutation and later mutations introduced extra positive charges on the spike RBD and resulted in higher transmissibility, likely due to stronger binding with the highly negatively charged ACE2. Consequently, many studies have been devoted to understanding the molecular mechanism of spike protein binding with the ACE2 receptor. Most of the theoretical studies, however, have been done on isolated proteins. ACE2 is a transmembrane protein; thus, it is important to understand the interaction of spike proteins with ACE2 in a lipid matrix. In this study, the adsorption of ACE2 and spike (N501Y) RBD at a lipid/water interface was studied using the heterodyne-detected vibrational sum frequency generation (HD-VSFG) technique. The technique is a non-linear optical spectroscopy which measures vibrational spectra of molecules at an interface and provides information on their structure and orientation. It is found that ACE2 is effectively adsorbed at the positively charged 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP) lipid monolayer via electrostatic interactions. The adsorption of ACE2 at the DPTAP monolayer causes a reorganization of interfacial water (D2O) from the D-down to the D-up orientation, indicating that the originally positively charged DPTAP interface becomes negatively charged due to ACE2 adsorption. The negatively charged interface (DPTAP/ACE2) allows further adsorption of positively charged spike RBD. HD-VSFG spectra in the amide I region show differences for spike (N501Y) RBD adsorbed at D2O, DPTAP, and DPTAP/ACE2 interfaces. A red shift observed for the spectra of spike RBD/DPTAP suggests that spike RBD oligomers are formed upon contact with DPTAP lipids.

Widely Tunable Femtosecond Sources with Continuously Tailorable Bandwidth Enabled by Self‐Phase Modulation

AbstractGenerating ultrafast pulses with better spectrotemporal control is crucial for optimizing and characterizing nonlinear light–matter responses, yet it is limited by the gain bandwidth of laser media or the phase‐matching geometry of nonlinear processes. This work proposes a simple approach to independently manage a femtosecond source's spectral location and bandwidth. Self‐phase‐modulation‐enabled spectral broadening is first analyzed, which is potentially energy‐scalable using hollow‐core capillaries or multipass cells. It is demonstrated that the outmost lobes in the broadened spectrum show different dependencies on the initial pulse energy and duration. A simple yet effective toy model is introduced that successfully predicts broadband spectral tuning, and the impact of other nonlinear effects, dispersion, and input pulse asymmetry on the experimental scenario is also discussed. Thus a fiber‐based versatile source is demonstrated, which is compressible down to its transform‐limit duration, as short as 12.2 fs centered at 920 nm. In addition, bandwidth‐dependent third‐harmonic generation spectroscopy is performed from a dielectric metasurface with an optimized nonlinear response, and the dependency of laser bandwidth and pulse duration is investigated on the signal‐to‐background ratio of two‐photon images. It is believed that this demonstration will advance the investigation of bandwidth‐dependent nonlinear spectroscopy and microscopy.

Probing lithium mobility at a solid electrolyte surface

Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 s state to hybridized Li-s/Ti-d orbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions.

Amplification of a terahertz wave via stimulated Raman scattering.

Extremely strong terahertz (THz) waves are desperately demanded for investigating nonlinear physics, spectroscopy, and imaging in the THz range. However, traditional crystal-/semiconductor-based THz sources have limitations of reaching extremely high amplitude due to the damage threshold of devices. Here, by introducing Raman amplification to the THz range, we propose a novel, to the best of our knowledge, scheme to amplify THz waves in plasma. A long-pulse CO2 pump laser transfers its energy to a multicycle, 10-THz seed in a two-step plasma. By one-dimensional simulations, a 0.87-GV/m, 1.2-ps-duration THz seed is amplified to 10 GV/m in a 5.7-mm-long plasma with an amplification efficiency approaching 1%. The method provides a new technology to manipulate the intensity of THz waves.

A multi-mode super-fano mechanism for enhanced third harmonic generation in silicon metasurfaces

We present strong enhancement of third harmonic generation in an amorphous silicon metasurface consisting of elliptical nano resonators. We show that this enhancement originates from a new type of multi-mode Fano mechanism. These ‘Super-Fano’ resonances are investigated numerically in great detail using full-wave simulations. The theoretically predicted behavior of the metasurface is experimentally verified by linear and nonlinear transmission spectroscopy. Moreover, quantitative nonlinear measurements are performed, in which an absolute conversion efficiency as high as ηmax ≈ 2.8 × 10−7 a peak power intensity of 1.2 GW cm−2 is found. Compared to an unpatterned silicon film of the same thickness amplification factors of up to ~900 are demonstrated. Our results pave the way to exploiting a strong Fano-type multi-mode coupling in metasurfaces for high THG in potential applications.

Pulse overlap artifacts and double quantum coherence spectroscopy.

The double quantum coherence (DQC) signal in nonlinear spectroscopy gives information about the many-body correlation effects not easily available by other methods. The signal is short-lived, consequently, a significant part of it is generated during the pulse overlap. Since the signal is at two times the laser frequency, one may intuitively expect that the pulse overlap-related artifacts are filtered out by the Fourier transform. Here, we show that this is not the case. We perform explicit calculations of phase-modulated two-pulse experiments of a two-level system where the DQC is impossible. Still, we obtain a significant signal at the modulation frequency, which corresponds to the DQC, while the Fourier transform over the pulse delay shows a double frequency. We repeat the calculations with a three-level system where the true DQC signal occurs. We conclude that with realistic dephasing times, the pulse-overlap artifact can be significantly stronger than the DQC signal. Our results call for great care when analyzing such experiments. As a rule of thumb, we recommend that only delays larger than 1.5 times the pulse length should be used.

Extracting the sample response function from experimental two-dimensional terahertz-infrared-visible spectra.

Terahertz molecular motions are often probed by high-frequency molecular oscillators in different types of non-linear vibrational spectroscopy. Recently developed two-dimensional terahertz-infrared-visible spectroscopy allows direct measuring of this coupling and, thus, obtaining site-specific terahertz vibrational spectrum. However, these data are affected by the intensity and phase of the employed laser pulses. In this work, we develop a method of extracting sample response-representing solely physical properties of a material-from experimental spectra. Using dimethyl sulfoxide as a model molecule to verify this method, we measure the coupling between C-H stretch vibration of its methyl groups and terahertz intramolecular twist and wagging modes.