Linear Spectrum Research Articles

A parametric frequency domain approach to analysis and design of critical design parameters of nonlinear energy harvesting systems: Parametric output spectrum and power generation functions

Nonlinear energy harvesting systems have been extensively studied which usually involve quite a few critical design parameters to determine. However, a straightforward parametric design method for such a purpose is still far from developed. Traditional methods with harmonic balance or numerical simulation usually cannot reveal a straightforward relationship between the energy harvesting performance and system parameters, and in most cases face relatively large computational costs during parametric studies. To this aim, a novel Volterra series-based frequency domain method is established in this study with respect to a typical nonlinear harvesting system. A concise parametric characteristic approach, namely the linear and nonlinear characteristic output spectrum (lnCOS) method, is thus proposed to achieve parametric characteristic expression for the nonlinear output frequency response and power generation function (PGF) of the system, referred to as the lnCOS function and the Parametric-PGF respectively. Compared with the harmonic balance method, the vibration responses/power generation can be obtained in a more straightforward way without solving complex algebraic equations, and the lnCOS method directly links the power outputs to critical system parameters in a concise parametric way. It is for the first time to provide explicit expressions for vibration responses and power generations with respect to structural parameters of a nonlinear energy harvesting system, which cannot be achieved in a traditional way. Based on the obtained explicit expressions of the lnCOS function/Parametric-PGF, the sensitivity analysis of vibration response and power generation with respect to structural parameters can be directly performed. Our work provides an efficient way to characterize both the linear and nonlinear effects on a nonlinear energy harvesting system and demonstrates an efficient approach to the analysis and design of nonlinear energy harvesting systems.

All‐Dielectric Terahertz Metasurface with Giant Extrinsic Chirality for Dual‐Mode Sensing

Metasurface‐based sensors, with their planar compact structure and excellent sensing performance, have become one of the emerging technologies in metasurface and nanophotonics in recent years. In particular, chiral metasurfaces show unique advantages for chiral molecule detection and enantiomer identification. Herein, a scheme of dual‐mode sensing based on all‐dielectric terahertz metasurface via chiral and achiral spectroscopy is proposed. The proposed achiral meta‐atoms show great extrinsic chirality. The transmitted linearly polarized spectrum and the circular dichroism (CD) can be used as the sensing indicator under normal and oblique incidence of the terahertz waves, respectively. Among them, the working mode based on linear polarization spectrum only needs to measure the transmission spectrum once, which means wide applicability. The other mode using CD can eliminate the achiral terahertz absorption of the analyte through multiple measurements and has a higher signal‐to‐noise ratio. The results show that the maximum refractive index–frequency change rates of the two operating modes are −128.5 GHz/RIU and −124.7 GHz/RIU, respectively. In addition, there are two resonant peaks available in both working states, for both high‐precision and wide‐range refractive index detection. This new scheme is expected to be applied in industrial fields such as terahertz biochemical detection.

Vibrational spectral dynamics and ion-probe interactions of the hydrogen-bonded liquids in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

We investigate ion-probe interactions within the molecular liquid, examine dynamics, and interpret the vibrational spectral dynamics of the mixtures of ionic liquid, 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIm][NTf2] with the probes of varying alkyl chain length – HOD, methanol-d4, ethanol-d6. Structural analysis depicts pronounced interactions of the oxygen atom of HOD with the corresponding anionic oxygen site rather than the hydrogen atom located at the two-position of the imidazolium ring. Our computed frequency distribution for each of the probes in IL exhibits similarity with the experimental linear FT-IR spectrum. We further performed the orientational anisotropy calculations; the ion reorientation plays a significant role in determining the transport properties in ILs. The results of rotational anisotropy of the O-D bond vector reflect the hydrogen bond length-scale fluctuations and collective reorientation associated with the complete structural reorganization of the probe modes. Our findings in this study agree well with the earlier experimental and simulation studies.

Dark energy survey year 3 results: cosmological constraints from the analysis of cosmic shear in harmonic space

ABSTRACT We present cosmological constraints from the analysis of angular power spectra of cosmic shear maps based on data from the first three years of observations by the Dark Energy Survey (DES Y3). Our measurements are based on the pseudo-Cℓ method and complement the analysis of the two-point correlation functions in real space, as the two estimators are known to compress and select Gaussian information in different ways, due to scale cuts. They may also be differently affected by systematic effects and theoretical uncertainties, making this analysis an important cross-check. Using the same fiducial Lambda cold dark matter model as in the DES Y3 real-space analysis, we find ${S_8 \equiv \sigma _8 \sqrt{\Omega _{\rm m}/0.3} = 0.793^{+0.038}_{-0.025}}$, which further improves to S8 = 0.784 ± 0.026 when including shear ratios. This result is within expected statistical fluctuations from the real-space constraint, and in agreement with DES Y3 analyses of non-Gaussian statistics, but favours a slightly higher value of S8, which reduces the tension with the Planck 2018 constraints from 2.3σ in the real space analysis to 1.5σ here. We explore less conservative intrinsic alignments models than the one adopted in our fiducial analysis, finding no clear preference for a more complex model. We also include small scales, using an increased Fourier mode cut-off up to $k_{\rm max}={5}\, {h}\, {\rm Mpc}^{-1}$, which allows to constrain baryonic feedback while leaving cosmological constraints essentially unchanged. Finally, we present an approximate reconstruction of the linear matter power spectrum at present time, found to be about 20 per cent lower than predicted by Planck 2018, as reflected by the lower S8 value.

A new class of out-gap discrete solitons in binary waveguide arrays.

We analytically and numerically investigate beyond-band discrete solitons, which present a completely new class of stable localized out-gap solitons with detunings being located beyond the two bands of the linear plane waves in a periodic binary waveguide array. Each of the even and odd components of these discrete solitons does not change its sign across the transverse direction of the binary waveguide array. The even and odd components of these newly found discrete solitons can be approximately presented by two hyperbolic secant functions with the only difference in their peaks. This approximation is especially good in the low-intensity regime in which the detuning of these solitons can asymptotically reach the two limits of a linear spectrum. These distinguishing features altogether make the newly found discrete solitons different from all other classes of discrete solitons investigated earlier in binary waveguide arrays. Two transformation rules for constructing even and odd components of these discrete solitons are also found for various combinations of signs of the propagation mismatch σ and nonlinear coefficient γ.

Solutions of several theory and technique problems in high-space-resolving hotspot electron temperature diagnosis techniques in inertial confinement fusion

In implosion experiments, bremsstrahlung radiation ratios of broad-energy-band x-ray emission intensities (sampled by Ross pair) and narrow-energy-band x-ray emission intensities (sampled by multilayer) are typically used to extract the hotspot electron temperature. The latter method could potentially be more accurate because it does not require any additional theoretical arithmetic. However, the boundary conditions of the energy band, drastic influence on the measured electron temperature resulting from response differences of recording devices in the energy band, evident impact from uncertainties of the detector aiming, and coordinate interrelations for the two narrow-energy-band x-ray images have not been explored. These problems should be overcome to obtain the accurate hotspot electron temperature using the narrow-energy-band x-ray emission intensities method. This study solves the problems indicated above by exploring a diagnosis technique to extract the accurate hotspot electron temperature. In particular, we determine that the effect of the response differences and uncertainties could be ignored when the width of the sampled narrow energy band is approximately ±0.5 keV in the linear spectrum response regions of the imaging plate, and the reflectivity of the multilayer is uniform and constant in that energy band and the viewing field of the detector (≥±110 µm). This study is the first to consider the linear spectrum response of the imaging plate in different energy regions, eliminating the effect of the response differences. Finally, the maximal emission intensities in the two recorded-energy-band x-ray images can be used for coordinate interrelation.

Nonlinear optical properties and optimization strategies of D-π-A type phenylamine derivatives in the near-infrared region

Modifying simple molecular structures to significantly improve nonlinear optical (NLO) performance is a primary prerequisite for scientific research. Based on the four phenylamine derivatives reported in previous studies, we designed four organic nonlinear molecules by changing the acceptor group and π-linker. (Time-dependent) density functional theory (DFT/TD-DFT) was performed on molecular geometry optimization, the contribution of π electrons to the bond order, linear and two-photon absorption (TPA) spectra, the intra-molecular charge transfer matrix (CTM), and NLO coefficients. These aspects were considered to analyze in detail how the structural modification of acceptors and π-linkers affects NLO characteristics. The three modification methods were: adding a carbonyl group at the junction of the π-linker and the acceptor group, adding a carbonyl group and a nitrogen atom to the acceptor group, and replacing the quinolinone with a pyrenyl group as the π-linker. The latter two methods can significantly reduce the excitation energy and enhance the intensity of intra-molecular charge transfer during the two-photon transition. The maximum TPA cross-sections and wavelengths of the designed molecules are DPPM (84722.6 GM, 815.7 nm) and DDPM (21600.6 GM, 781.3 nm). These two molecules have large TPA cross-sections in the near-infrared region, which renders them as possible NLO materials with broad application prospects.

Evolution mapping: a new approach to describe matter clustering in the non-linear regime

ABSTRACT We present a new approach to describe statistics of the non-linear matter density field that exploits a degeneracy in the impact of different cosmological parameters on the linear dimensionless matter power spectrum, $\Delta ^2_{\rm L}(k)$. We classify all cosmological parameters into two groups, shape parameters, which determine the shape of $\Delta ^2_{\rm L}(k)$, and evolution parameters, which only affect its amplitude at any given redshift. With this definition, the time evolution of $\Delta ^2_{\rm L}(k)$ in models with identical shape parameters but different evolution parameters can be mapped from one to the other by relabelling the redshifts that correspond to the same clustering amplitude, which we characterize by the linear mass fluctuation in spheres of radius $12\, {\rm Mpc}$, σ12(z). We use N-body simulations to show that the same evolution-mapping relation gives a good description of the non-linear power spectrum, the halo mass function, or the full density field. The deviations from the exact degeneracy are the result of the different structure formation histories experienced by each model to reach the same clustering amplitude and can be accurately described in terms of differences in the suppression factor g(a) = D(a)/a. These relations can be used to drastically reduce the number of parameters required to describe the cosmology dependence of the power spectrum. We show how this can help to speed up the inference of parameter constraints from cosmological observations. We also present a new design of an emulator of the non-linear power spectrum whose predictions can be adapted to an arbitrary choice of evolution parameters and redshift.

Accelerating Large-Scale-Structure data analyses by emulating Boltzmann solvers and Lagrangian Perturbation Theory.

The linear matter power spectrum is an essential ingredient in all theoretical models for interpreting large-scale-structure observables. Although Boltzmann codes such as CLASS or CAMB are very efficient at computing the linear spectrum, the analysis of data usually requires 10 4-10 6evaluations, which means this task can be the most computationally expensive aspect of data analysis. Here, we address this problem by building a neural network emulator that provides the linear theory (total and cold) matter power spectrum in about one millisecond with ≈0.2%(0.5%) accuracy over redshifts z ≤ 3 (z ≤ 9), and scales10 -4≤ k [ h Mpc -1] < 50. We train this emulator with more than 200,000 measurements, spanning a broad cosmological parameter space that includes massive neutrinos and dynamical dark energy. We show that the parameter range and accuracy of our emulator is enough to get unbiased cosmological constraints in the analysis of a Euclid-like weak lensing survey. Complementing this emulator, we train 15 other emulators for the cross-spectra of various linear fields in Eulerian space, as predicted by 2nd-order Lagrangian Perturbation theory, which can be used to accelerate perturbative bias descriptions of galaxy clustering. Our emulators are specially designed to be used in combination with emulators forthe nonlinear matter power spectrum and for baryonic effects, all of which are publicly available at http://www.dipc.org/bacco.

Beware of fakeν’s: The effect of massive neutrinos on the nonlinear evolution of cosmic structure

Massive neutrinos suppress the growth of cosmic structure on small, nonlinear scales. It is thus often proposed that using statistics beyond the power spectrum can tighten constraints on the neutrino mass by extracting additional information from these nonlinear scales. We study the information content regarding neutrino mass at the field level, quantifying how much of this information arises from the difference in nonlinear evolution between a cosmology with one fluid [cold dark matter (CDM)] and two fluids ($\mathrm{CDM}+\text{neutrinos}$). We do so by running two $N$-body simulations, one with and one without massive neutrinos, both with the same phases, and matching their linear power spectrum at a given low redshift. This effectively isolates the information encoded in the linear initial conditions from the nonlinear cosmic evolution. We demonstrate that, for $k\ensuremath{\lesssim}1\text{ }\text{ }h/\mathrm{Mpc}$, and for a single redshift, there is negligible difference in the real-space CDM field between the two simulations. This suggests that all the information regarding neutrino mass is in the linear power spectrum set by the initial conditions. Thus, any probe based on the CDM field alone will have negligible constraining power beyond that which exists at the linear level over the same range of scales. Consequently, any probe based on the halo field will contain little information beyond the linear power. We find similar results for the matter field responsible for weak lensing. We also demonstrate that there may be much information beyond the power spectrum in the 3D matter field; however, this is not observable in modern surveys via dark matter halos or weak lensing. Finally, we show that there is additional information to be found in redshift space.

Spectral densities and absorption spectra of the core antenna complex CP43 from photosystem II.

Besides absorbing light, the core antenna complex CP43 of photosystem II is of great importance in transferring excitation energy from the antenna complexes to the reaction center. Excitation energies, spectral densities, and linear absorption spectra of the complex have been evaluated by a multiscale approach. In this scheme, quantum mechanics/molecular mechanics molecular dynamics simulations are performed employing the parameterized density functional tight binding (DFTB) while the time-dependent long-range-corrected DFTB scheme is applied for the excited state calculations. The obtained average spectral density of the CP43 complex shows a very good agreement with experimental results. Moreover, the excitonic Hamiltonian of the system along with the computed site-dependent spectral densities was used to determine the linear absorption. While a Redfield-like approximation has severe shortcomings in dealing with the CP43 complex due to quasi-degenerate states, the non-Markovian full second-order cumulant expansion formalism is able to overcome the drawbacks. Linear absorption spectra were obtained, which show a good agreement with the experimental counterparts at different temperatures. This study once more emphasizes that by combining diverse techniques from the areas of molecular dynamics simulations, quantum chemistry, and open quantum systems, it is possible to obtain first-principle results for photosynthetic complexes, which are in accord with experimental findings.

Tunable multiwavelength Erbium-doped fiber laser based on in-fiber Fabry-Perot interferometer fiber Bragg gratings in linear and ring cavity configurations

Multiwavelength Erbium-doped fiber laser (MWEDFL) in the ring and linear cavities operating at 1.5-μm wavelength region was demonstrated. The multiwavelength fiber laser comprises a 3-m Erbium-doped fiber as an active gain medium, an in-fiber Fabry-Perot interferometer Fiber Bragg Gratings (FPI FBG) as a filter, and a 10-km dispersion compensating fiber (DCF) as a nonlinear gain medium. A comparison investigation was conducted. The MWEDFL in the linear cavity generates 12 stable lasing lines, with an optical signal-to-noise ratio (OSNR) of 45 dB. In the case of MWEDFL operated in a ring cavity, 8 stable lasing lines were generated, with an OSNR of 47 dB. The free spectral range (FSR) of 0.08 nm was measured for the FPI FBG in both linear and ring cavities MWEDFL spectrum. Besides, the stability measurement was conducted for 150 min for both MWEDFL cavities. Both lasers had a peak power fluctuation of less than 1.0 dB and negligible wavelength drifts below 0.1 nm. Furthermore, the wavelength tunability of MWEDFL in both configurations was performed by heating the FPI FBG from 28 °C to 100 °C. At the temperature of 100 °C, the MWEDFL shows a wavelength shift of 1.0 nm, and this can be further increased by heating the FPI FBG to its highest temperature limit. This MWEDFL employs in-fiber FPI FBG offers a compact, highly tunable, and simple design applicable for optical communications and optical sensing applications.

Exact simulation of pigment-protein complexes unveils vibronic renormalization of electronic parameters in ultrafast spectroscopy

The primary steps of photosynthesis rely on the generation, transport, and trapping of excitons in pigment-protein complexes (PPCs). Generically, PPCs possess highly structured vibrational spectra, combining many discrete intra-pigment modes and a quasi-continuous of protein modes, with vibrational and electronic couplings of comparable strength. The intricacy of the resulting vibronic dynamics poses significant challenges in establishing a quantitative connection between spectroscopic data and underlying microscopic models. Here we show how to address this challenge using numerically exact simulation methods by considering two model systems, namely the water-soluble chlorophyll-binding protein of cauliflower and the special pair of bacterial reaction centers. We demonstrate that the inclusion of the full multi-mode vibronic dynamics in numerical calculations of linear spectra leads to systematic and quantitatively significant corrections to electronic parameter estimation. These multi-mode vibronic effects are shown to be relevant in the longstanding discussion regarding the origin of long-lived oscillations in multidimensional nonlinear spectra.

Solution structures and ultrafast vibrational energy dissipation dynamics in cyclotetramethylene tetranitramine.

Steady-state and time-resolved infrared (IR) studies of cyclotetramethylene tetranitramine (HMX) were carried out, using the asymmetric nitro-stretch as probe, to investigate its solution structures and vibrational energy transfer processes in pure dimethyl sulfoxide (DMSO) and in a DMSO/water mixture. A linear IR spectrum in the nitro-stretching mode region shows two major bands and one minor band in DMSO but changes to the two major bands mainly picture when adding water as an antisolvent of HMX, suggesting a transition from well-solvated and less perfect β-conformation to a less-solvated and close-to-perfect β-conformation. The latter bears a similar asymmetric nitro-stretch vibration profile to the β-polymorph in the crystal form. Density functional theory computations of the nitro-stretching vibrations suggest that HMX in DMSO may be in a NO2 group rotated β-conformation. Two-dimensional IR cross-peak intensity reveals intramolecular energy transfer between the axial and equatorial nitro-groups in the β-HMX on the ps time scale, which is slightly faster in the mixed solvent case. The importance of water as an antisolvent in influencing the equilibrium solvation structure, as well as the vibrational and orientational relaxation dynamics of HMX, is discussed.

Above bandgap one-photon excitation induced nonlinear absorption behavior of InTe

In an attempt to investigate the nonlinear absorption properties of amorphous InTe semiconductors, three different thicknesses of 30 nm, 60 nm and 90 nm thin films were deposited by the vacuum evaporation method. Bandgap energies and Urbach energies were obtained from the linear absorption spectrum. While the change in thickness and doping led to slight changes in bandgap energies as 0.08 eV, significant increases in Urbach energies were obtained for thicker and doped films. A theoretical model accounting one photon absorption, excited state absorption, and saturation of each process was utilized to derive the transmittance in open aperture Z-scan data. The values of nonlinear absorption coefficient and saturation intensity threshold were obtained from the model and the interplay between excited state absorption and saturable absorption was explained by proposing an energy band diagram containing the contribution of defect states to the nonlinear absorption behavior of amorphous semiconductors.

Grid-based calculations of redshift-space matter fluctuations from perturbation theory: UV sensitivity and convergence at the field level

Perturbation theory (PT) has been used to interpret the observed nonlinear large-scale structure statistics at the quasi-linear regime. To facilitate the PT-based analysis, we have presented the GridSPT algorithm, a grid-based method to compute the nonlinear density and velocity fields in standard perturbation theory (SPT) from a given linear power spectrum. Here, we further put forward the approach by taking the redshift-space distortions into account. With the new implementation, we have, for the first time, generated the redshift-space density field to the fifth order and computed the next-to-next-to-leading order (2 loop) power spectrum and the next-to-leading order (1 loop) bispectrum of matter clustering in redshift space. By comparing the result with corresponding analytical SPT calculation and $N$-body simulations, we find that the SPT calculation (A) suffers much more from the UV sensitivity due to the higher-derivative operators and (B) deviates from the $N$-body results from the Fourier wavenumber smaller than real space $k_{\rm max}$. Finally, we have shown that while Pad\'e approximation removes spurious features in morphology, it does not improve the modeling of power spectrum and bispectrum.

Sequence effect of as-welded and HFMI-treated transverse attachments under variable loading with linear spectrum

It has been shown in several studies that methods to improve the fatigue strength of welded structures, such as high-frequency impact treatment (HFMI), can increase the fatigue life of welded joints [1–6]. The results of these investigations led to current guidelines and recommendations for the fatigue assessment of HFMI-treated welded joints. Nevertheless, in practice, there are reservations regarding the efficiency of HFMI-treated welded steel joints under variable amplitude loading. Recent results [7] from studies on transverse attachments of the material S355 and S700 under variable amplitude loading show that the fatigue strength increasing effect of the HFMI-treatment is maintained compared to the as-welded state. The aim of this study is to analyse the sequence effect on the fatigue strength of HFMI-treated transverse attachments and to validate the applicability of linear damage accumulation hypotheses for the design of as-welded and HFMI-treated welded details. In this paper, fatigue test results with random variable amplitude loading (VAL) and high-low VAL and low–high VAL with linear spectrum for the two states as-welded (AW) and HFMI-treated joints will be presented.

A Study of Second‐Order Susceptibility in Digital Alloy‐Grown InAs/AlSb Multiple Quantum Wells

AbstractA preliminary measurement of the second‐order nonlinear optical susceptibility of symmetric, coupled, InAs/AlSb multiple quantum well (MQW) structures is acquired through optical second‐harmonic generation (SHG) at fundamental wavelength 1.55 µm. High quality crystalline MQW structures of variable thickness and corresponding bulk AlSb control samples are achieved using a digital alloy epitaxial growth technique that avoids cluster formation and phase segregation. All samples are grown in between a GaSb cap and substrate layer. To isolate SHG from the MQW (or control) layers of interest from cap and substrate contributions, a multilayer optical response matrix model is built and independently tested by accurately reproducing linear reflectivity spectra. While a simplified response matrix analysis of SHG based solely on bulk χ(2)s does not reproduce the distinct SHG responses of the two sets of samples, the inclusion of an additional interface SHG contribution leads to a successful fit of the data and implies . The results demonstrate a proof‐of‐concept quantification of χ(2) in symmetric MQWs and suggest the possibility of engineering χ(2) in these structures, particularly with the introduction of well asymmetries.

Expanding the Utility of 4‐cyano‐L‐phenylalanine as a Vibrational Reporter

Unnatural amino acids (UAAs) have become useful tools for understanding protein structure and local environments. One of the most commonly used vibrational reporter UAAs to study local protein hydration environments is 4‐cyano‐L‐phenylalanine (pCNF) due to the position and sensitivity of the nitrile symmetric stretching frequency as well as the ability to efficiently incorporate this UAA site‐specifically into proteins using the Amber codon suppression methodology. Additionally, pCNF provides promise to function as a distance reporter when coupled with two‐dimensional infrared (2D IR) spectroscopy. Here, a number of superfolder green fluorescent protein (sfGFP) constructs have been generated with pCNF site‐specifically incorporated at two unique sites simultaneously. The pairs of sites were selected to permit the nitrile symmetric stretching frequency of pCNF at each site to be spectrally resolved. The temperature dependent linear IR spectra of these sfGFP constructs with two pCNF UAAs incorporated will be presented, illustrating that the nitrile groups are in different local environments. Preliminary X‐ray crystal structures of these sfGFP constructs will be presented to probe if the UAAs resulted in a structural perturbation and to determine the distance between the nitrile groups of the two pCNF UAAs in each structure. These results will serve as the basis for and calibration of employing pCNF in future 2D IR spectroscopic studies to extract the distances between these two groups based upon coupling between them.

Dynamics in tris(pentafluoroethyl)trifluorophosphate (FAP) anion based ionic liquids: A 2D-IR study with tungsten hexacarbonyl

Ultrafast two-dimensional infrared spectroscopy (2D-IR) measurements for tungsten hexacarbonyl, W(CO)6, has been performed in two fluoroalkylphosphate ([FAP])-based ultrahigh hydrophobic, ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate ([EMIM][FAP]) and 1-(hexyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]) to probe their local structure and dynamics. To understand the effect of FAP anion on the dynamics, a relatively less hydrophobic [PF6-] anion has been introduced in the form of [HMIM][PF6]. While the linear IR spectra records some influence of anion in terms of spectral shifts, the alkyl chain length of the cation seems to have no significant influence on the spectral peak position; and even the spectral broadening is found to be in the similar range. Further, vibrational population relaxation dynamics and vibrational anisotropy decay also does not show any significant variation due to difference in constituent of these ionic liquids as well as its solvent properties, such as, viscosity. Finally, 2D-IR spectra show large variation in the spectral shapes with waiting times, which qualitatively remains similar in all the tested ionic liquids. The frequency-fluctuation correlation function measured from 2D-IR spectra displays a bi-exponential decay with the shorter time-constant dependent on the identity of the anion, and has been attributed to the ion-rattling motion, whereas, the longer component has been found to be invariant with the identity of ionic liquid, and has been attributed to ion-cage motions which is in line with previous MD simulations as well as previous experimental measurements, using ionic vibrational probe. Overall, 2D-IR spectroscopy, in combination with this neutral and hydrophobic probe, W(CO)6 provides a unique opportunity to understand the local structural dynamics of this ultrahigh hydrophobic ionic liquid which are otherwise not accessible by hitherto explored ionic vibrational probes.