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Aquatic athletes not only face common headache etiologies similar to the general population and land-based athletes but also experience their own unique pathology. Posture, aquatic pressure, equipment, and even marine animals pose as unique causes to head pain in the aquatic athlete. Common head pain pathologies seen in the aquatic athlete include tension-type headaches, migraines, cluster headaches, and compressive headaches, including supraorbital neuralgia. Creating a thorough but focused differential diagnosis for head pain in the aquatic athlete can be a difficult and overwhelming task for some. We review both the common and not-so-common etiologies of head pain in the aquatic athlete and suggest a simple framework for assessment and treatment to diagnose and treat head pain in this specific population.

The dynamics of excess protons in the protic ionic liquid ethylammonium formate (EAF) have been investigated from femtosecond to microseconds using visible pump mid-infrared probe spectroscopy. The pH-jump following visible photoexcitation of a photoacid (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt, HPTS) results in proton transfer to the formate of the EAF. The proton transfer predominantly occurs over picoseconds through a pre-formed hydrogen-bonded complex between HPTS and EAF. We investigate the longer range and longer timescale proton transport processes in the ionic liquid by obtaining the ground-state conjugate base (RO-) dynamics from the congested transient-infrared spectra. The spectral kinetics indicate that the protons diffuse only a few solvent shells from the parent photoacid before recombining with RO-. A kinetic isotope effect of near unity (kH/kD~1) suggests vehicular transfer and transport of excess protons in this ionic liquid. Our findings provide a comprehensive insight into the complete photoprotolytic cycle of excess protons in a protic ionic liquid.

The infrared spectra of EDTA complexed with Ca2+ and Mg2+ contain, to date, unidentified vibrational bands. This study assigns the peaks in the linear and two-dimensional infrared spectra of EDTA, with and without either Ca2+ or Mg2+ ions. Two-dimensional infrared spectroscopy and DFT calculations reveal that, in both the presence and absence of ions, the carboxylate symmetric stretch and the terminal CH bending vibrations mix. We introduce a method to calculate participation coefficients that quantify the contribution of the carboxylate symmetric stretch, CH wag, CH twist, and CH scissor in the 1400-1550 cm-1 region. With the help of participation coefficients, we assign the 1400-1430 cm-1 region to the carboxylate symmetric stretch, which can mix with CH modes. We assign the 1000-1380 cm-1 region to CH twist modes, the 1380-1430 cm-1 region to wag modes, and the 1420-1650 cm-1 region to scissor modes. The difference in binding geometry between the carboxylate-Ca2+ and carboxylate-Mg2+ complex manifests as new diagonal and cross-peaks between the mixed modes in the two complexes. The small Mg2+ ion binds EDTA tighter than the Ca2+ ion, which causes a redshift of the COO symmetric stretches of the sagittal carboxylates. Energy decomposition analysis further characterizes the importance of electrostatics and deformation energy in the bound complexes.

Ultrafast two-dimensional infrared spectroscopy (2D-IR) and Fourier transform infrared spectroscopy (FTIR) were used to measure carbon dioxide (CO2) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]), cross-linked low-molecular-weight poly(ethylene glycol) diacrylate (PEGDA), and an ion gel composed of a 50 vol % blend of the two. The center frequency of the antisymmetric stretch, ν3, of CO2 shifts monotonically to lower wavenumbers with increasing polymer content, with the largest line width in the ion gel (6 cm-1). Increasing polymer content slows both spectral diffusion and vibrational energy relaxation (VER) rates. An unexpected excited-state absorbance peak appears in the 2D-IR of cross-linked PEGDA due to VER from the antisymmetric stretch into the bending mode, ν2. Thirty-two response functions are necessary to describe the observed features in the 2D-IR spectra. Nonlinear least-squares fitting extracts both spectral diffusion and VER rates. In the ion gel, CO2 exhibits spectral diffusion dynamics that lie between that of the pure compounds. The kinetics of VER reflect both fast excitation and de-excitation of the bending mode, similar to the ionic liquid (IL), and slow overall vibrational population relaxation, similar to the cross-linked polymer. The IL-like and polymer-like dynamics suggest that the CO2 resides at the interface of the two components in the ion gel.

The infrared spectra of EDTA complexed with Ca

Ultrafast two-dimensional infrared spectroscopy (2D-IR) and Fourier transform infrared spectroscopy (FTIR) were used to measure carbon dioxide (CO

© 2020 American Chemical Society. Vibrational spectroscopy is an essential tool in chemical analyses, biological assays, and studies of functional materials. Over the past decade, various coherent nonlinear vibrational spectroscopic techniques have been developed and enabled researchers to study time-correlations of the fluctuating frequencies that are directly related to solute-solvent dynamics, dynamical changes in molecular conformations and local electrostatic environments, chemical and biochemical reactions, protein structural dynamics and functions, characteristic processes of functional materials, and so on. In order to gain incisive and quantitative information on the local electrostatic environment, molecular conformation, protein structure and interprotein contacts, ligand binding kinetics, and electric and optical properties of functional materials, a variety of vibrational probes have been developed and site-specifically incorporated into molecular, biological, and material systems for time-resolved vibrational spectroscopic investigation. However, still, an all-encompassing theory that describes the vibrational solvatochromism, electrochromism, and dynamic fluctuation of vibrational frequencies has not been completely established mainly due to the intrinsic complexity of intermolecular interactions in condensed phases. In particular, the amount of data obtained from the linear and nonlinear vibrational spectroscopic experiments has been rapidly increasing, but the lack of a quantitative method to interpret these measurements has been one major obstacle in broadening the applications of these methods. Among various theoretical models, one of the most successful approaches is a semiempirical model generally referred to as the vibrational spectroscopic map that is based on a rigorous theory of intermolecular interactions. Recently, genetic algorithm, neural network, and machine learning approaches have been applied to the development of vibrational solvatochromism theory. In this review, we provide comprehensive descriptions of the theoretical foundation and various examples showing its extraordinary successes in the interpretations of experimental observations. In addition, a brief introduction to a newly created repository Web site (http://frequencymap.org) for vibrational spectroscopic maps is presented. We anticipate that a combination of the vibrational frequency map approach and state-of-the-art multidimensional vibrational spectroscopy will be one of the most fruitful ways to study the structure and dynamics of chemical, biological, and functional molecular systems in the future.

Molecular dynamics (MD) simulations validated against two-dimensional infrared (2D-IR) measurements of CO2 in an imidazolium-based ionic liquid have revealed new insights into the mechanism of CO2 solvation. The first solvation shell around CO2 has a distinctly quadrupolar structure, with strong negative charge density around the CO2 carbon atom and positive charge density near the CO2 oxygen atoms. When CO2 is modeled without atomic charges (thus removing its strong quadrupole moment), its solvation shell weakens and changes significantly into a structure that is similar to that of N2 in the same liquid. The solvation shell of CO2 evolves more quickly when its quadrupole is removed, and we find evidence that solvent cage dynamics is measured by 2D-IR spectroscopy. We also find that the solvent cage evolution of N2 is similar to that of CO2 with no atomic charges, implying that the weaker quadrupole of N2 is responsible for its higher diffusion and lower absorption in ionic liquids.

This work elucidates the molecular binding mechanism of CO2 in [C4C1IM][PF6] ionic liquid (IL) and its interplay with the CO2 asymmetric stretch frequency ν3, and establishes computational protocols for the reliable construction of spectroscopic maps for simulating ultrafast 2D-IR data of CO2 solvated in ILs. While charge transfer drives the static frequency shift between different ionic liquids (J. Chem. Phys. 2015, 142, 212425), we find here that electrostatic and Pauli repulsion effects dominate the dynamical frequency shift between different geometries sampled from the finite-temperature dynamics within a single ionic liquid. This finding is also surprising because dispersion interactions dominate the CO2–IL interaction energies, but are comparably constant across different geometries. An important practical consequence of this finding is that density functional theory is expected to be sufficiently accurate for constructing potential energy surfaces for CO2 in [C4C1IM][PF6], as needed for accurate an...

The primary challenge for connecting molecular dynamics (MD) simulations to linear and two-dimensional infrared measurements is the calculation of the vibrational frequency for the chromophore of interest. Computing the vibrational frequency at each time step of the simulation with a quantum mechanical method like density functional theory (DFT) is generally prohibitively expensive. One approach to circumnavigate this problem is the use of spectroscopic maps. Spectroscopic maps are empirical relationships that correlate the frequency of interest to properties of the surrounding solvent that are readily accessible in the MD simulation. Here, we develop a spectroscopic map for the asymmetric stretch of CO2 in the 1-butyl-3-methylimidazolium hexafluorophosphate ([C4C1im][PF6]) ionic liquid (IL). DFT is used to compute the vibrational frequency of 500 statistically independent CO2-[C4C1im][PF6] clusters extracted from an MD simulation. When the map was tested on 500 different CO2-[C4C1im][PF6] clusters, the c...

Using ultrafast two-dimensional infrared spectroscopy (2D-IR), a vibrational probe (thiocyanate, SCN-) was used to investigate the hydrogen bonding network of a molten salt (ethyl-ammonium nitrate, EAN) compared to that of H2O. The 2D-IR experiments were performed in both parallel () and perpendicular () conditions along with temperature dependence for both EAN (14-130 ˚C) and H2O (5-89 ˚C). With polarization control, the frequency fluctuation correlation function can be separated into structural and rotational components. An Arrhenius analysis lead to independent activation energies for the isotropic, and anisotropic signals, structural spectral diffusion, and rotational induced spectral diffusion. The rotational Eas were similar for both EAN and H2O suggesting that SCN- is experiencing a similar jump model, i.e. where hydrogen bond reorientation is dominated by large angular jumps stemming from molecular rotation dynamics. The frequency pre-factors, however, were different where the more rigid and vicious EAN had a slower rate. Furthermore, the 2D-IR anisotropy and vibrational relaxation rates of EAN are frequency dependent, revealing that SCN- experiences two subensembles. We suggest that the sub-ensemble with a faster rotational timescale correlates to SCN- with more, weaker hydrogen bonds, and the sub-ensemble with a slower rotational timescale correlates to SCN- with a stronger, more directional hydrogen bond.

Two-dimensional infrared spectroscopy (2D-IR) probes the local solvent structure and dynamics of the nu3 mode (BH antisymmetric stretch) of borohydride (BH4- ) in aqueous solution. The 2D-IR spectra of the BH stretches have broad and overlapping bands. Vibrational energy relaxation occurs on a 2 ps timescale. Energy that is initially deposited in BH stretching modes and directly in the solvent generates a long lived hot ground state. Before the hot ground state appears, some indications of intramolecular vibrational energy redistribution are observed. The solvent viscosity was varied (1.5–6 cP) by increasing the hydroxide concentration (0.1–7 M). Within the vibrational lifetime of the BH stretching modes, the rate of structural relaxation slows proportionally to the viscosity due to the overlap of the ions’s solvation shells.

Using ultrafast two-dimensional infrared spectroscopy (2D-IR), a vibrational probe (thiocyanate, SCN-) was used to investigate the hydrogen bonding network of the protic ionic liquid ethyl-ammonium nitrate (EAN) in comparison to H2O. The 2D-IR experiments were performed in both parallel (⟨ZZZZ⟩) and perpendicular (⟨ZZXX⟩) polarizations at room temperature. In EAN, the non-Gaussian lineshape in the FTIR spectrum of SCN- suggests two sub-ensembles. Vibrational relaxation rates extracted from the 2D-IR spectra provide evidence of the dynamical differences between the two sub-ensembles. We support the interpretation of two sub-ensembles with response function simulations of two overlapping bands with different vibrational relaxation rates and, otherwise, similar dynamics. The measured rates for spectral diffusion depend on polarization, indicating reorientation-induced spectral diffusion (RISD). A model of restricted molecular rotation (wobbling in a cone) fully describes the observed spectral diffusion in EAN. In H2O, both RISD and structural spectral diffusion contribute with similar timescales. This complete characterization of the dynamics at room temperature provides the basis for the temperature-dependent measurements in Paper II of this series.

In recent years, interest in carbon capture and sequestration has led to numerous investigations of the ability of ionic liquids to act as recyclable CO2-sorbent materials. Herein, we investigate the structure and dynamics of a model physisorbing ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4C1Im][PF6]), from the perspective of CO2 using two-dimensional (2D) IR spectroscopy and molecular dynamics simulations. A direct comparison of experimentally measured and calculated 2D IR line shapes confirms the validity of the simulations and spectroscopic calculations. Taken together, the simulations and experiments reveal new insights into the interactions of a CO2 solute with the surrounding ionic liquid and how these interactions manifest in the 2D IR spectra. In particular, higher CO2 asymmetric stretch vibrational frequencies are associated with softer, less populated solvent cages and lower frequencies are associated with tighter, more highly populated solvent cages. The CO2 interacts most...

Molecular dynamics (MD) simulations validated against two-dimensional infrared (2D-IR) measurements of CO

Ionic liquid (IL)-surfactant complexes have significance both in applications and fundamental research, but their underlying dynamics are not well understood. We apply polarization-controlled two-dimensional infrared spectroscopy (2D-IR) to study the dynamics of [BMIM][SCN]/surfactant/solvent model systems. We examine the effect of the choice of surfactants and solvent, and the IL-to-surfactant ratio (W-value), with a detailed analysis of the orientation and structural dynamics of each system. Different surfactants create very different environments for the entrapped ILs, ranging from a semi-static micro-environment to a fluxional environment that evolves even faster than the bulk IL. The oil-phase also clearly affects the microscopic dynamics. The anisotropy decay for entrapped ILs completes within 10 ps, which is similar to free thiocyanate ion in water, while a significant reorientation-induced spectral diffusion (RISD) effect is observed. The entrapped ionic liquid are highly dynamic for all W-values, and no core-shell structure is observed. We hypothesize that, instead of an ionic liquid-reverse micelle (IL-RM), the microscopic structure of this system is small colloidal dispersions or pairs of IL and surfactants. A detailed analysis of the polarization-controlled 2D-IR spectra of AOT system reveals a potential ion-exchange mechanism.

Ultrafast two-dimensional infrared spectroscopy (2D-IR) of thiocyanate ([SCN]−) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]) and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1C1(2)im][NTf2]) ionic liquids probes local structure and dynamics as a function of the water content, solute counterion, and solute concentration. The 2D-IR spectra of the water-saturated ionic liquids resolve two distinct kinds of dynamics. This dynamical heterogeneity is explained as two subensembles, one with and one without a water molecule in the first solvation shell. When the countercation is K+, ion pairs between K+ and [SCN]− that persist for >100 ps are detected by long-lasting vibrational frequency correlations. The observed dynamics are invariant to [SCN]− concentration, which indicates that the [SCN]− does not cluster in ionic liquid solution. Taken together, these results are consistent with a picture of thiocyanate as a local probe that can interrogate ultrafast structure and dynamics at a small spatial scale in ionic liquids.

The stereochemistry and the reaction rates of bimolecular nucleophilic substitution reactions involving azides in ionic liquids are governed by solute–solvent interactions. Two-dimensional ultrafast vibrational spectroscopy (2D-IR) shows that the picosecond dynamics of inorganic azides are substantially slower than organic azides in a series of homologous imidazolium ionic liquids. In water, both organic and inorganic azides spectrally diffuse with a ∼2 ps time constant. In the aprotic solvent tetrahydrofuran, both kinds of azides spectrally diffuse on a timescale >5 ps. In ionic liquids, like 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), organic azides spectrally diffuse with a 2–4 ps time constant, and inorganic azides spectrally diffuse with a >40 ps time constant. Such a striking difference suggests that neutral (organic) and charged (inorganic) azides are incorporated in the ionic liquids with different solvation structures.