Ultrafast Infrared Research Articles

Unveiling the Structural and Dynamic Characteristics of Concentrated LiNO3 Aqueous Solutions through Ultrafast Infrared Spectroscopy and Molecular Dynamics Simulations.

Highly concentrated aqueous electrolytes have attracted a significant amount of attention for their potential applications in lithium-ion batteries. Nevertheless, a comprehensive understanding of the Li+ solvation structure and its migration within electrolyte solutions remains elusive. This study employs linear vibrational spectroscopy, ultrafast infrared spectroscopy, and molecular dynamics (MD) simulations to elucidate the structural dynamics in LiNO3 solutions by using intrinsic and extrinsic vibrational probes. The N-O stretching vibrations of NO3- exhibit a distinct spectral splitting, attributed to its asymmetric interaction with the surrounding solvation structure. Analysis of the vibrational relaxation dynamics of intrinsic and extrinsic probes, in combination with MD simulations, reveals cage-like networks formed through electrostatic interactions between Li+ and NO3-. This microscopic heterogeneity is reflected in the intertwined arrangement of ions and water molecules. Furthermore, both vehicular transport and structural diffusion assisted by solvent rearrangement for Li+ were analyzed, which are closely linked with the bulk concentration.

Understanding the [NiFe] Hydrogenase Active Site Environment through Ultrafast Infrared and 2D-IR Spectroscopy of the Subsite Analogue K[CpFe(CO)(CN)2] in Polar and Protic Solvents.

The [CpFe(CO)(CN)2]- unit is an excellent structural model for the Fe(CO)(CN)2 moiety of the active site found in [NiFe] hydrogenases. Ultrafast infrared (IR) pump-probe and 2D-IR spectroscopy have been used to study K[CpFe(CO)(CN)2] (M1) in a range of protic and polar solvents and as a dry film. Measurements of anharmonicity, intermode vibrational coupling strength, vibrational relaxation time, and solvation dynamics of the CO and CN stretching modes of M1 in H2O, D2O, methanol, dimethyl sulfoxide, and acetonitrile reveal that H-bonding to the CN ligands plays an important role in defining the spectroscopic characteristics and relaxation dynamics of the Fe(CO)(CN)2 unit. Comparisons of the spectroscopic and dynamic data obtained for M1 in solution and in a dry film with those obtained for the enzyme led to the conclusion that the protein backbone forms an important part of the bimetallic active site environment via secondary coordination sphere interactions.

Tailoring the Biobased Polythiourethane Crosslinking Networks with Flame-Retardancy and Remote Ultrafast Infrared “Welding” Performance

The common solution for developing thermosetting polymers with self-healing performance is to introduce covalent adaptive networks into the crosslinked systems. However, most of the self-healing polymers were conducted in “integral...

Influence of Internal Bond Rotation on Ultrafast IR Anisotropy Measurements and the Internal Rotational Potential.

Measurement of molecular orientation relaxation using ultrafast infrared (IR) pump-probe experiments is widely used to understand the properties of liquids and other systems. In the simplest situation, the anisotropy decay is a single exponential reflecting diffusive orientational relaxation. However, the anisotropy decay is frequently biexponential. The faster component is caused by solvent caging restricting angular sampling until constraint release permits all angles to be sampled. Here, we describe another mechanism that limits the range of sampling, i.e., sampling of a restricted range of angles via internal bond reorientation on a rotational potential surface with barriers. If the internal angular sampling occurs faster than the entire molecule's diffusive orientational relaxation, it will produce a fast component of anisotropy decay with a cone angle determined by the shape of the internal rotation potential. We studied four molecules to illustrate the effects of internal bond rotations on anisotropy decay. The molecules are p-chlorobenzonitrile, phenylselenocyanate, phenylthiocyanate, and 2-nitrophenylselenocyante in the solvent N,N-dimethylformamide. The CN stretch is used as the IR chromophore. p-Chlorobenzonitrile does not have internal rotation; its anisotropy decays as a single exponential. The other three have bent geometries and internal rotation of the moieties containing the CN occurs; the anisotropies decay as biexponentials. The faster of the two decays can be understood in terms of motions on the rotational potential surface. A method is developed for extracting the intramolecular rotational potential surface by employing a modification of the harmonic cone model, and the results are compared to density functional theory calculations.

Investigating Intramolecular H Atom Transfer Dynamics in β-Diketones with Ultrafast Infrared Spectroscopies and Theoretical Modeling.

The vibrational signatures and ultrafast dynamics of the intramolecular H-bond in a series of β-diketones are investigated with 2D IR spectroscopy and computational modeling. The chosen β-diketones exhibit a range of H atom donor-acceptor distances and asymmetry along the H atom transfer coordinate that tunes the intramolecular H-bond strength. The species with the strongest H-bonds are calculated to have very soft H atom potentials, resulting in highly red-shifted OH stretch fundamental frequencies and dislocation of the H atom upon vibrational excitation. These soft potentials lead to significant coupling to the other normal mode coordinates and give rise to the very broad vibrational signatures observed experimentally. The 2D IR spectra in both the OH and OD stretch regions of the light and deuterated isotopologues reveal broadened and long-lived ground-state bleach signatures of the vibrationally hot molecules. Polarization-sensitive transient absorption measurements in the OH and OD stretch regions reveal notable isotopic differences in orientational dynamics. Orientational relaxation was measured to occur on ∼600 fs and ∼2 ps time scales for the light and deuterated isotopologues, respectively. The orientational dynamics are interpreted in terms of activated H/D atom transfer events driven by collective intramolecular structural rearrangements.

Performance evaluation of an Ultra-Fast IR Detector for Astronomy Transients

In this work, we present the design of an ultra-fast IR (InfraRed) detector for the search of astronomical transients. Time-domain astronomy is a field in continuous growth in the last years, with interest in detectors with nanosecond performance, in order to observe potential fast transients with the time scale of GRBs (Gamma Ray Bursts) and FRBs (Fast Radio Bursts). An ultra-fast temporal detector based on HgCdTe photoconductors is under development in Italy, at the Frascati National Laboratory of the National Institute of Nuclear Physics, by tests at SINBAD, the DAFNE infrared beamline. The detector will be used for mid-IR observations together with a ground-based reflecting telescope or launched on a scientific balloon.

Chain-like Structures Facilitate Li+ Transport in Concentrated Aqueous Electrolytes: Insights from Ultrafast Infrared Spectroscopy and Molecular Dynamics Simulations.

Highly concentrated aqueous electrolytes have attracted attention due to their unique applications in lithium ion batteries (LIBs). However, the solvation structure and transport mechanism of Li+ cations at concentrated concentrations remain largely unexplored. To address this gap in knowledge, we employ ultrafast infrared spectroscopy and molecular dynamics (MD) simulations to reveal the dynamic and spatial structural heterogeneity in aqueous lithium chloride (LiCl) solutions. The coupling between the reorientation dynamics of the extrinsic probe and the macroscopic viscosity in aqueous LiCl solutions was analyzed using the Stokes-Einstein-Debye (SED) equations. MD simulations reveal that the Cl- and Li+ form chain-like structures through electrostatic interactions, supporting the vehicular migration of Li+ through the chain-like structure. The concentration dependent conductivity of the LiCl solution is well reproduced, where Li(H2O)2+ and Li(H2O)3+ are the dominant species that contribute to the conduction of Li+. This study is expected to establish correlations between ion pair structures and macroscopic properties.

Ion/Water Network Structural Dynamics in Highly Concentrated Lithium Chloride and Lithium Bromide Solutions Probed with Ultrafast Infrared Spectroscopy

The structural dynamics of highly concentrated LiCl and LiBr aqueous solutions were observed from 1-4 to 1-16 water molecules per ion pair using ultrafast polarization-selective pump-probe (PSPP) experiments on the OD stretch of dilute HOD. At these high salt concentrations, an extended ion/water network exists with complex structural dynamics. Population decays from PSPP experiments highlight two distinct water components. From the frequency-dependent amplitudes of the decays, the spectra of hydroxyls bound to halides and to water oxygens are obtained, which are not observable in the FT-IR spectra. PSPP experiments also measure frequency-dependent water orientational relaxation. At short times, wobbling dynamics within a restricted angular cone occurs. At high concentrations, the cone angles are dependent on frequency (hydrogen bond strength), but at higher water concentrations (>10 waters per ion pair), there is no frequency dependence. The average cone angle increases as the ion concentration decreases. The slow time constant for complete HOD orientational relaxation is independent of concentration but slower in LiCl than in LiBr. Comparison to structural MD simulations of LiCl from the literature indicates that the loss of the cone angle wavelength dependence and the increase in the cone angles as the concentration decreases occur as the prevalence of large ion/water clusters gives way to contact ion pairs.

Dynamics of Acrylamide Hydrogels, Polymers, and Monomers in Water Measured with Optical Heterodyne-Detected Optical Kerr Effect Spectroscopy.

The ultrafast dynamics of acrylamide monomers (AAm), polyacrylamide (PAAm), and polyacrylamide hydrogels (PAAm-HG) in water were studied using optical heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy. Previous ultrafast infrared (IR) measurements of the water dynamics showed that at the same concentration of the acrylamide moiety, AAm, PAAm, and PAAm-HG exhibited identical water dynamics and that these dynamics slowed with increasing concentration. In contrast to the IR measurements, OHD-OKE experiments measure the dynamics of both the water and the acrylamide species, which occur on different time scales. In this study, the dynamics of all the acrylamide systems slowed with increasing concentration. We found that AAm exhibits tetraexponential decays, the longest component of which followed Debye-Stokes-Einstein behavior except for the highest concentration, 40% (w/v). Low concentrations of PAAm followed a single power law decay, while high concentrations of PAAm and all concentrations of PAAm-HG decayed with two power laws. The highest concentrations, 25% and 40%, of PAAm and PAAm-HG showed nearly identical dynamics. We interpreted this result as reflecting a similar extent of chain-chain interactions. At low concentrations, PAAm displays non-Markovian, single-chain dynamics (single power law), but PAAm displays entangled chain-chain interactions at high concentrations (two power laws). PAAm-HG has chain-chain interactions at all concentrations that arise from the cross-linking. At high concentrations, the dynamics of the entangled of PAAm become identical within error as those of the cross-linked PAAm-HG.

Understanding 2D-IR Spectra of Hydrogenases: A Descriptive and Predictive Computational Study

[NiFe] hydrogenases are metalloenzymes that catalyze the reversible cleavage of dihydrogen (H2), a clean future fuel. Understanding the mechanism of these biocatalysts requires spectroscopic techniques that yield insights into the structure and dynamics of the [NiFe] active site. Due to the presence of CO and CN− ligands at this cofactor, infrared (IR) spectroscopy represents an ideal technique for studying these aspects, but molecular information from linear IR absorption experiments is limited. More detailed insights can be obtained from ultrafast nonlinear IR techniques like IRpump-IRprobe and two-dimensional (2D-)IR spectroscopy. However, fully exploiting these advanced techniques requires an in-depth understanding of experimental observables and the encoded molecular information. To address this challenge, we present a descriptive and predictive computational approach for the simulation and analysis of static 2D-IR spectra of [NiFe] hydrogenases and similar organometallic systems. Accurate reproduction of experimental spectra from a first-coordination-sphere model suggests a decisive role of the [NiFe] core in shaping the enzymatic potential energy surface. We also reveal spectrally encoded molecular information that is not accessible by experiments, thereby helping to understand the catalytic role of the diatomic ligands, structural differences between [NiFe] intermediates, and possible energy transfer mechanisms. Our studies demonstrate the feasibility and benefits of computational spectroscopy in the 2D-IR investigation of hydrogenases, thereby further strengthening the potential of this nonlinear IR technique as a powerful research tool for the investigation of complex bioinorganic molecules.

Probing Lattice Dynamics in Two-Dimensional Inorganic Pseudohalide Perovskites with Ultrafast Infrared Spectroscopy

Probing Lattice Dynamics in Two-Dimensional Inorganic Pseudohalide Perovskites with Ultrafast Infrared Spectroscopy

Si/SnSe-Nanorod Heterojunction with Ultrafast Infrared Detection Enabled by Manipulating Photo-Induced Thermoelectric Behavior.

Photothermal detectors have attracted tremendous research interest in uncooled infrared imaging technology but with a relatively slow response. Here, Si/SnSe-nanorod (Si/SnSe-NR) heterojunctions are fabricated as a photothermal detector to realize high-performance infrared response beyond the bandgap limitation. Vertically standing SnSe-NR arrays are deposited on Si by a sputtering method. Through manipulating the photoinduced thermoelectric (PTE) behavior along the c-axis, the Si/SnSe-NRs heterojunction exhibits a unique four-stage photoresponse with a high photoresponsivity of 106.3 V W-1 and high optical detectivity of 1.9 × 1010 cm Hz1/2 W-1 under 1342 nm illumination. Importantly, an ultrafast infrared photothermal response is achieved with the rise/fall time of 11.3/258.7 μs. Moreover, the coupling effect between the PTE behavior and external thermal excitation enables an improved response by 288.4%. The work not only offers a new strategy to develop high-speed photothermal detectors but also performs a deep understanding of the PTE behavior in a heterojunction system.

Water Dynamics and Structure of Highly Concentrated LiCl Solutions Investigated Using Ultrafast Infrared Spectroscopy.

In highly concentrated salt solutions, the water hydrogen bond (H-bond) network is completely disrupted by the presence of ions. Water is forced to restructure as dictated by the water-ion and ion-ion interactions. Using ultrafast polarization-selective pump-probe (PSPP) spectroscopy measurements of the OD stretch of dilute HOD, we demonstrate that the limited water-water H-bonding present in concentrated lithium chloride solutions (up to four waters per ion pair) is, on average, stronger than that occurring in bulk water. Furthermore, information on the orientational dynamics and the angular restriction of water H-bonded to both water oxygens and chloride anions was obtained through analysis of the frequency-dependent anisotropy decays. It was found that, when the salt concentration increased, the water showed increasing restriction and slowing at frequencies correlated with strong H-bonding. The angular restriction of the water molecules and strengthening of water-water H-bonds are due to the formation of a water-ion network not present in bulk water and dilute salt solutions. The structural evolution of the ionic medium was also observed through spectral diffusion of the OD stretch using 2D IR spectroscopy. Compared to bulk water, there is significant slowing of the biexponential spectral diffusion dynamics. The slowest component of the spectral diffusion (13 ps) is virtually identical to the time for complete reorientation of HOD measured with the PSPP experiments. This result suggests that the slowest component of the spectral diffusion reflects rearrangement of water molecules in the water-ion network.

Time-Domain Vibrational Action Spectroscopy of Cryogenically Cooled, Messenger-Tagged Ions Using Ultrafast IR Pulses.

Herein, we present the initial steps toward developing a framework that will enable the characterization of photoinitiated dynamics within large molecular ions in the gas phase with temporal and energy resolution. We combine the established techniques of tag-loss action spectroscopy on cryogenically trapped molecular ions with ultrafast vibrational spectroscopy by measuring the linear action spectrum of N2-tagged protonated diglycine (GlyGlyH+·N2) with an ultrafast infrared (IR) pulse pair. The presented time-domain data demonstrate that the excited-state vibrational populations in the tagged parent ions are modulated by the ultrafast IR pulse pair and encoded through the messenger tag-loss action response. The Fourier transform of the time-domain action interferograms yields the linear frequency-domain vibrational spectrum of the ion ensemble, and we show that this spectrum matches the linear spectrum collected in a traditional manner using a frequency-resolved IR laser. Time- and frequency-domain interpretations of the data are considered and discussed. Finally, we demonstrate the acquisition of nonlinear signals through cross-polarization pump-probe experiments. These results validate the prerequisite first steps of combining tag-loss action spectroscopy with two-dimensional IR spectroscopy for probing dynamics in gas-phase molecular ions.

Cationic Effects on the Structural Dynamics of the Metal Ion-Crown Ether Complexes Investigated by Ultrafast Infrared Spectroscopy.

It is usually believed that the binding affinity and selectivity of an alkali metal ion with crown ether are defined by the size matching model. However, the underlying mechanism of the specific host-guest interactions and the structural dynamics of the metal ions confined in the cavity of the crown ethers in the solutions are still not clear. In this report, a series of alkali thiocyanate salts (XSCN; X = Li, Na, K, and Cs) complexed with 18-crown-6 (a typical crown ether) in the chloroform solutions were studied by the polarization-selective infrared pump-probe spectroscopy and the ultrafast two-dimensional infrared (2D IR) spectroscopy. The SCN- counteranions were employed as the local vibrational probe to reveal the specific host-guest interactions in the crown ether complexes. The rotational dynamics and spectral diffusion of SCN- vibration were both measured by ultrafast IR spectroscopy, and it was found that the metal cations hosted by the crown ethers can have a pronounced effect on the rotational dynamics of the counteranions. The reorientational time constants of the SCN- vibration in the complexation follow the order Li+ > Na+ > K+ ≃ Cs+. More importantly, the spectral diffusion dynamics of SCN-, which quantifies the decay of the correlation of the frequency fluctuations in the complexation, was also affected by the metal ions but showed a different order of cationic effect. A detailed analysis of the 2D IR data showed that the spectral diffusion of SCN- counteranion clearly decayed with two different time scales in the complex of 18-crown-6 with K+. The 3-4-fold slowdown in spectral diffusion indicated that the fluctuation of SCN- vibrational transition frequency was strongly affected by the K+ cation due to the geometric constraint imposed by the crown ether. The results should help the researchers to unravel the specific host-guest interactions and further reveal the origination of the binding selectivity of crown ether for metal cations in the condensed phases from the perspective of structural dynamics.

Control of Polymorphic Properties of Multivalent Vanadium Oxide Thin Films

In this study, VxOy thin films were deposited on borosilicate glass substrates using direct current (DC) magnetron sputtering. The optoelectronic thermochromic properties of the resulting multiphase vanadium oxide thin films were investigated. As-deposited (at 280 °C) films were annealed at 350, 450, and 500 °C in an oxygen atmosphere for 30 min in a tube furnace to improve the crystallinity. Structural analysis indicated the formation of a mixed-phase vanadium oxide film consisting of VO2(B), V4O9, and V2O5 phases on the amorphous substrate after annealing above 350 °C. The results showed that the semiconductor-to-metallic phase transition temperature of the vanadium oxide film increased from 48 to 63 °C with increasing annealing temperatures. The sample annealed at 450 °C exhibited the highest variation in the infrared (IR) transmittance (ΔTIR = 28.42%) and the resistivity switch decreased by two orders of magnitude (1.4 × 10–1–2.3 × 10–3 Ω/cm). The thermal treatment temperature affected the width of the thermal hysteresis loop (HLW) and slope stiffness. A narrower HLW of 1.9 °C and a sharp slope stiffness of 8.74 were obtained for the sample annealed at 500 °C. The slope stiffness plays an important role in the fabrication of ultrafast tunable energy-saving smart windows and IR switches.

Free Volume Element Sizes and Dynamics in Polystyrene and Poly(methyl methacrylate) Measured with Ultrafast Infrared Spectroscopy.

The size, size distribution, dynamics, and electrostatic properties of free volume elements (FVEs) in polystyrene (PS) and poly(methyl methacrylate) (PMMA) were investigated using the Restricted Orientation Anisotropy Method (ROAM), an ultrafast infrared spectroscopic technique. The restricted orientational dynamics of a vibrational probe embedded in the polymer matrix provides detailed information on FVE sizes and their probability distribution. The probe's orientational dynamics vary as a function of its frequency within the inhomogeneously broadened vibrational absorption spectrum. By characterizing the degree of orientational restriction at different probe frequencies, FVE radii and their probability distribution were determined. PS has larger FVEs and a broader FVE size distribution than PMMA. The average FVE radii in PS and PMMA are 3.4 and 3.0 Å, respectively. The FVE radius probability distribution shows that the PS distribution is non-Gaussian, with a tail to larger radii, whereas in PMMA, the distribution is closer to Gaussian. FVE structural dynamics, previously unavailable through other techniques, occur on a ∼150 ps time scale in both polymers. The dynamics involve FVE shape fluctuations which, on average, conserve the FVE size. FVE radii were associated with corresponding electric field strengths through the first-order vibrational Stark effect of the CN stretch of the vibrational probe, phenyl selenocyanate (PhSeCN). PMMA displayed unique measured FVE radii for each electric field strength. By contrast, PS showed that, while larger radii correspond to unique and relatively weak electric fields, the smallest measured radii map onto a broad distribution of strong electric fields.

Composition-Dependent Hydrogen-Bonding Motifs and Dynamics in Brønsted Acid-Base Mixtures.

In recent years the interaction of organophosphates and imines, which is at the core of Brønsted acid organocatalysis, has been established to be based on strong ionic hydrogen bonds. Yet, besides the formation of homodimers consisting of two acid molecules and heterodimers consisting of one acid and one base, also multimeric molecular aggregates are formed in solution. These multimeric aggregates consist of one base and several acid molecules. The details of the intermolecular bonding in such aggregates, however, have remained elusive. To characterize composition-dependent bonding and bonding dynamics in these aggregates, we use linear and nonlinear infrared (IR) spectroscopy at varying molar ratios of diphenyl phosphoric acid and quinaldine. We identify the individual aggregate species, giving rise to the structured, strong, and very broad infrared absorptions, which span more than 1000 cm–1. Linear infrared spectra and density functional theory calculations of the proton transfer potential show that doubly ionic intermolecular hydrogen bonds between the acid and the base lead to absorptions which peak at ∼2040 cm–1. The contribution of singly ionic hydrogen bonds between an acid anion and an acid molecule is observed at higher frequencies. As common to such strong hydrogen bonds, ultrafast IR spectroscopy reveals rapid, ∼ 100 fs, dissipation of energy from the proton transfer coordinate. Yet, the full dissipation of the excess energy occurs on a ∼0.8–1.1 ps time scale, which becomes longer when multimers dominate. Our results thus demonstrate the coupling and collectivity of the hydrogen bonds within these complexes, which enable efficient energy transfer.

Amorphous polymer dynamics and free volume element size distributions from ultrafast IR spectroscopy

A method for measuring the size and size probability distribution of free volume regions in polymeric materials using ultrafast infrared (IR) polarization-selective pump-probe experiments is presented. Measurements of the ultrafast dynamics of a vibrational probe (the CN stretch of phenyl selenocyanate) in poly(methyl methacrylate) show that the probe dynamics are highly confined. The degree of confinement was found to be both time-dependent and dependent on the vibrational frequency of the probe molecule. The experiments demonstrate that different vibrational frequencies correspond to distinct subensembles of probe molecules that have different dynamic properties determined by their local structural environments. By combining the degree of dynamical confinement with the molecular size of the probe molecule, the free volume element size probability distribution was determined and found to be in good agreement with the best established experimental measure of free volume. The relative probability of a free volume element size is determined by the amplitude of the nitrile absorption spectrum at the frequency of the measurement. The inhomogeneous broadening of the spectrum was linked to the vibrational Stark effect, which permits site selectivity. The observed dynamics at each frequency were then associated with a different size free volume element and distinct local electric field. The multiple timescales observed in the pump-probe experiments were connected to local structural fluctuations of the free volume elements.

Optimization of a multi-TW few-cycle 1.7-µm source based on Type-I BBO dual-chirped optical parametric amplification.

This paper presents the optimization of a dual-chirped optical parametric amplification (DC-OPA) scheme for producing an ultrafast intense infrared (IR) pulse. By employing a total energy of 0.77 J Ti:sapphire pump laser and type-I BBO crystals, an IR pulse energy at the center wavelength of 1.7 µm exceeded 0.1 J using the optimized DC-OPA. By adjusting the injected seed spectrum and prism pair compressor with a gross throughput of over 70%, the 1.7-µm pulse was compressed to 31 fs, which resulted in a peak power of up to 2.3 TW. Based on the demonstration of the BBO type-I DC-OPA, we propose a novel OPA scheme called the "dual pump DC-OPA" for producing a high-energy IR pulse with a two-cycle duration.