Real-time and high-throughput Raman signal extraction and processing in CARS hyperspectral imaging.

We present a new collection of processing techniques, collectively "factorized Kramers-Kronig and error correction" (fKK-EC), for (a) Raman signal extraction, (b) denoising, and (c) phase- and scale-error correction in coherent anti-Stokes Raman scattering (CARS) hyperspectral imaging and spectroscopy. These new methods are orders-of-magnitude faster than conventional methods and are capable of real-time performance, owing to the unique core concept: performing all processing on a small basis vector set and using matrix/vector multiplication afterwards for direct and fast transformation of the entire dataset. Experimentally, we demonstrate that a 703026 spectra image of chicken cartilage can be processed in 70 s (≈ 0.1 ms / spectrum), which is ≈ 70 times faster than with the conventional workflow (≈7.0 ms / spectrum). Additionally, we discuss how this method may be used for machine learning (ML) by re-using the transformed basis vector sets with new data. Using this ML paradigm, the same tissue image was processed (post-training) in ≈ 33 s, which is a speed-up of ≈ 150 times when compared with the conventional workflow.

The polarizability response of a glass-forming liquid reveals intrabasin motion and interbasin transitions on a potential energy landscape.

Potential energy landscape (PEL) concepts have been useful in conceptualizing the effects of intermolecular interactions on dynamic and thermodynamic properties of liquids and glasses. "Basins", or regions of reduced potential energy associated with locally preferred molecular packing are important PEL features. The molecular configurations at the bottom of these basins are referred to as inherent structures (ISs). Experimental methods for directly characterizing PEL features such as these are rare, largely relegating PEL concepts to theory and simulation studies, and impeding their exploration in real systems. Recently, we showed that quasielastic neutron scattering (QENS) data from propylene carbonate (PC) exhibit signatures of picosecond timescale motion that are consistent with intrabasin motion and interbasin transitions [Cicerone et al., J. Chem. Phys., 2017, 146, 054502]. Here we present optically-heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy studies on PC. The data exhibit signatures of motion within and transitions between basins that agree quantitatively with and extend the QENS results. We show that the librational component of the OKE response corresponds to intrabasin dynamics, and the enigmatic intermediate OKE response corresponds to interbasin transition events. The OKE data extend the measurement range of these parameters and reveal their utility in characterizing PEL features of real systems.

Empirical Analysis of Optical Kerr Effect Spectra: A Case for Constraint.

Ultrafast optical Kerr effect (OKE) spectroscopy is a widely used method for studying the depolarized, Raman-active intermolecular dynamics of liquids. Through appropriate manipulation of OKE data, it is possible to determine the reduced spectral density (RSD), which is the Bose-Einstein-corrected, low-frequency Raman spectrum with the contribution of diffusive reorientation removed. OKE RSDs for van der Waals liquids can often be fit well to an empirical function that is the sum of a Bucaro-Litovitz function and an antisymmetrized Gaussian (AG). Although these functions are not directly representative of specific intermolecular dynamics, the AG fit parameters can provide useful insights into the microscopic properties of liquids. Here we show that fits using the AG function are typically not well-determined, and that equally good results can be obtained with a wide range of fitting parameters. We propose the use of a physically motivated constraint on the amplitude of the AG function, and demonstrate that this constraint leads to more intuitive trends in the fit parameters for temperature-dependent RSDs in 1,3,5-trifluorobenzene and hexafluorobenzene.

How clean is the solvent you use to clean your optics? A vibrational sum-frequency-generation study.

Solvents for cleaning optics often come into contact with plastic and/or rubber during storage and transfer. To explore the effects that exposure to these materials can have on solvents, we used vibrational sum-frequency-generation spectroscopy to study a silica optic following cleaning with solvents that had come into contact with either low-density polyethylene, high-density polyethylene, or rubber. Our studies show that even brief contact of acetone, methanol, or isopropanol with plastic or rubber can cause otherwise pure solvents to leave a persistent residue.

Toward in Situ Measurement of the Density of Liquid Benzene Using Optical Kerr Effect Spectroscopy.

The high-frequency portion of the optical Kerr effect (OKE) spectrum of benzene shifts to higher frequency with decreasing temperature at constant pressure. This behavior has been interpreted previously in terms of an increase in librational frequencies due to the decrease in free volume with liquid densification. However, decreasing temperature also provides less access to the more repulsive portion of the intermolecular potential, which would cause the blue edge of the spectrum to red-shift. To explore the relative importance of these phenomena, molecular dynamics simulations of benzene are used to isolate the effects of temperature and density on the spectrum. The simulations show that, at constant density, the high-frequency portion of the spectrum shifts to lower frequency with decreasing temperature. In contrast, at constant temperature, the high-frequency portion of the spectrum shifts to higher frequency with increasing density. These results indicate that density plays a greater role in determining the position of the blue edge of the low-frequency Raman spectrum of benzene than does temperature. Empirical fits show that the effects of changing density or temperature are similar in experimental and simulated OKE spectra. Furthermore, line-shape analysis of simulated spectra under isochoric and isothermal conditions shows that the effects of density and temperature are separable, suggesting that OKE spectroscopy is a viable technique for in situ measurement of the density of van der Waals liquids.

Assessing Polarizability Models for the Simulation of Low-Frequency Raman Spectra of Benzene.

Optical Kerr effect (OKE) spectroscopy is a widely used technique for probing the low-frequency, Raman-active dynamics of liquids. Although molecular simulations are an attractive tool for assigning liquid degrees of freedom to OKE spectra, the accurate modeling of the OKE and the motions that contribute to it relies on the use of a realistic and computationally tractable molecular polarizability model. Here we explore how the OKE spectrum of liquid benzene, and the underlying dynamics that determines its shape, are affected by the polarizability model employed. We test a molecular polarizability model that uses a point anisotropic molecular polarizability and three other models that distribute the polarizability over the molecule. The simplest and most computationally efficient distributed polarizability model tested is found to be sufficient for the accurate simulation of the many-body polarizability dynamics of this liquid. We further find that the atomic-to-molecular polarizability transformation approximation [Hu et al. J. Phys. Chem. B 2008, 112, 7837-7849], used in conjunction with this distributed polarizability model, yields OKE spectra whose shapes differ negligibly from those calculated without this approximation, providing a substantial increase in computational efficiency.

Reorientation-induced spectral diffusion in vibrational sum-frequency-generation spectroscopy.

There is a growing appreciation that dynamic processes play an important role in determining the line shape in surface-selective, nonlinear spectroscopies such as vibrational sum-frequency-generation (VSFG). Here we analyze the influence that reorientation can have on VSFG spectra when the vibrational transition frequency is a function of orientation. Under these circumstances, reorientation-induced spectral diffusion (RISD) causes the underlying spectral line shape to become time dependent. Unlike previously reported mechanisms through which reorientation can contribute to the VSFG signal, RISD influences the line shape regardless of the degree of polarization of the Raman transition that is probed. We assess the impact of RISD on VSFG spectra using a model system of liquid acetonitrile at a silica interface. Comparison of delay-time-dependent VSFG spectra with simulations that employ static line shapes suggests that RISD contributes substantially to the spectra, particularly at delay times that are comparable to or greater than the probe pulse duration. The observed behavior is in qualitative agreement with a two-state RISD model that uses orientational distributions determined from previous molecular dynamics simulations.

Persistence of acetonitrile bilayers at the interface of acetonitrile/water mixtures with silica.

Previous experiments and simulations have shown that acetonitrile organizes into a lipid-like bilayer at the liquid/silica interface. Recent simulations have further suggested that this bilayer structure persists in mixtures of acetonitrile with water, even at low acetonitrile concentrations. This behavior is indicative of microscopic phase separation of these liquids near silica interfaces and may have important ramifications for the use of acetonitrile in chromatography and heterogeneous catalysis. To explore this phenomenon, we have used vibrational sum-frequency-generation spectroscopy to probe acetonitrile/water mixtures at a silica interface. Our spectra provide evidence that acetonitrile partitions to the hydrated silica interface even when the mole fraction of acetonitrile is as low as 10%. A blue shift is observed in the spectrum of the methyl symmetric stretch upon increasing water mole fraction, in agreement with vibrational spectra of bulk mixtures. Line shape analysis suggests that acetonitrile may exist in the form of bilayer patches at high water mole fractions.