Theoretical Calculation and Simulation of Peak Distortion of Absorption Spectra of Complex Mixtures.

Attenuated total reflection (ATR) spectroscopy in infrared is a standard tool used in most analytical labs, as it allows a rapid chemical analysis with virtually no sample preparation. However, when the sample contains materials with a high refractive index, special care must be taken as the resulting data may be severely biased. This article reports a theoretical approach to correcting distorted ATR spectra.

Developing Correction Methods by Revisiting the Concept of Effective Thickness in Attenuated Total Reflection Spectroscopy.

We propose a new way of deriving the effective thickness in attenuated total reflection (ATR) spectroscopy, initially introduced by Hansen and Harrick in 1965. While following Hansen's approach, our derivation is more straightforward and includes an intermediate approximation that more closely aligns with results derived from Fresnel's equations, particularly for organic and biological materials. Using this intermediate approximation, we present improved estimations for the effective thicknesses with - and -polarized light.

Combining Infrared Refraction and Attenuated Total Reflection Spectroscopy.

We have specified and obtained a ZnSe prism with an unconventional face angle cut to 30°. This prism, with internal incidence angles ranging from 30° to 48°, allows users to record internal reflection spectra below the critical angle and attenuated total reflection (ATR) spectra above the critical angle without the need to change optics or move or replace the sample. We demonstrate its capabilities using 102 spectra of benzyl benzoate taken with - and -polarization at different angles of incidence.

Understanding Advanced Attenuated Total Reflection Correction: The Low Absorbance Assumption.

We present an attenuated total reflection (ATR) correction scheme capable of rectifying ATR spectra while considering the polarization state for arbitrary angles of incidence, provided that this angle exceeds the critical angle for the entire ATR spectrum. Due to its reliance on the weak absorption approximation, it cannot achieve perfect correction of the ATR spectra. However, comprehending its functionality may offer valuable insights into the concept behind the weak absorption approximation.

Dispersion Analysis of Perpendicular Modes Using a Hybrid Two-Trace Two-Dimensional (2T2D) Smart Error Sum.

Using linear dichroism theory, one would assume that a z-cut of a uniaxial crystal is equivalent to an x-cut to determine the perpendicular component of the dielectric tensor and the corresponding oscillator parameters. However, Fresnel's equations show that the effect of interfaces in the form of the continuity relations of the different components of the electric field must be considered. A consequence of the continuity relations is that perpendicular modes increase less significantly in strength with increasing angle of incidence than expected.

Polarization-dependent effects in vibrational absorption spectra of 2D finite-size adsorbate islands on dielectric substrates.

In the last few years, infrared reflection-absorption spectroscopy (IRRAS) has become a standard technique to study vibrational excitations of molecules. These investigations are strongly motivated by potential applications in monitoring chemical processes. For a better understanding of the adsorption mechanism of molecules on dielectrics, the polarization-dependence of an interaction of infrared light with adsorbates on dielectric surfaces is commonly used.

Sophisticated Attenuated Total Reflection Correction Within Seconds for Unpolarized Incident Light at 45°.

The most common mid-infrared (MIR) attenuated total reflection (ATR) accessory has a nominal angle of incidence of 45° and does not have a polarizer. A spectrum recorded with such an accessory does not hold enough information for the sophisticated ATR correction of MIR spectra with strong peaks, which are often strongly affected by refractive index changes due to anomalous dispersion. Here we show that a 45° ATR spectrum recorded without a polarizer and the polarization angle for the same ATR Fourier transform infrared spectroscopy system provide enough information to determine the ATR -polarized spectrum.

Quantitative evaluation of IR and corresponding VCD spectra.

Classical electromagnetic theory applied to infrared (IR) and vibrational circular dichroism (VCD) spectra of chiral compounds can provide useful insights, such as the fact that the area of all bands of wavenumber-normalized absorbance above zero must be the same as the area below zero. Additionally, dispersion analysis based on wave optics and dispersion theory, which was extended by Born and Kuhn to include chiral substances, can be used to quantitatively describe the dielectric function and the chiral admittance functions that shape IR and VCD spectra. For dispersion analysis, pairs of coupled oscillators, with five different kinds of parameters, namely oscillator strength, damping, oscillator position, vertical distance between coupled oscillators, and the coupling constant are used to model the dielectric functions and chiral admittance functions.

The footprint of linear dichroism in infrared 2D-Correlation spectra.

On the level of the Bouguer-Beer-Lambert approximation, the effects introduced by linear dichroism into absorbance spectra can be simulated by classic linear dichroism theory. If wave optics and dispersion theory are employed, linear dichroism can be modelled with a 4x4 matrix formalism. For linear dichroism theory, the angle between polarization direction and transition moment can be seen as a perturbation which allows to calculate corresponding infrared 2D correlation spectra.

Dielectric metasurface-assisted cavity ring-down spectroscopy for thin-film circular dichroism analysis.

Chiral molecules show differences in their chemical and optical properties due to the different spatial arrangements of the atoms in the two enantiomers. A common way to optically differentiate them is to detect the disparity in the absorption of light by the two enantiomers, absorption circular dichroism (CD). However, the CD of typical molecules is very small, limiting the sensitivity of chiroptical analysis based on CD.

Understanding Refractive Index Changes in Homologous Series of Unbranched Organic Compounds Based on Beer's Law.

Changes of the refractive index for homologous series of hydrocarbons are usually plotted versus the density. While there is a clear linear dependence for alkanes and alkenes, the linearity deteriorates for homologous series with functional groups involving heteroatoms. The slope can even become negative, e.

Unveiling chiral optical constants of α-pinene and propylene oxide through ATR and VCD spectroscopy in the mid-infrared range.

Optical constants functions of analytes are indispensable for the effective design of plasmonic sensors. Such sensors are potentially able to enhance the sensitivity by several order of magnitudes which can greatly facilitate the determination of the generally weak spectral signals caused by vibrational circular dichroism. Accordingly, to demonstrate how to obtain these functions, we have determined the dielectric and chirality admittance functions of α-Pinene and Propylene oxide in the mid-infrared spectral range using attenuated total reflection and vibrational circular dichroism spectroscopy.

SpectIR-fluidics: completely customizable microfluidic cartridges for high sensitivity on-chip infrared spectroscopy with point-of-application studies on bacterial biofilms.

We present a generalizable fabrication method for a new class of analytical devices that merges virtually any microfluidic design with high-sensitivity on-chip attenuated total reflection (ATR) sampling using any standard Fourier transform infrared (FTIR) spectrometer. Termed "spectIR-fluidics", a major design feature is the integration of a multi-groove silicon ATR crystal into a microfluidic device, compared with previous approaches in which the ATR surface served as a structural support for the entire device. This was accomplished by the design, fabrication, and aligned bonding of a highly engineered ATR sensing layer, which con```tains a seamlessly embedded ATR crystal on the channel side and an optical access port that matched the spectrometer light path characteristics at the device exterior.

Simple, Fast and Convenient Magnetic Bead-Based Sample Preparation for Detecting Viruses via Raman-Spectroscopy.

We introduce a magnetic bead-based sample preparation scheme for enabling the Raman spectroscopic differentiation of severe acute respiratory syndrome coronavirus type 2 (SARS-CoV-2)-positive and -negative samples. The beads were functionalized with the angiotensin-converting enzyme 2 (ACE2) receptor protein, which is used as a recognition element to selectively enrich SARS-CoV-2 on the surface of the magnetic beads. The subsequent Raman measurements directly enable discriminating SARS-CoV-2-positive and -negative samples.

Dispersion related coupling effects in IR spectra on the example of water and Amide I bands.

We discuss coupling effects in infrared spectra which are caused by dispersion and local field effects. The first effect is instigated by changes of the refractive index due to absorption which have an impact on the strength of adjacent absorptions. The second effect is a consequence of the light-induced polarization of one molecule affecting neighboring ones.

The Global Polarity of Alcoholic Solvents and Water - Importance of the Collectively Acting Factors Density, Refractive Index and Hydrogen Bonding Forces.

The D quantity represents the hydroxyl group density of alcoholic solvents or water. D is purely physically defined by the product of molar concentration of the solvent (N) and the factor Σn=n×f which reflects the number n and position (f-factor) of the alcoholic OH groups per molecule. Whether the hydroxyl group is either primary, secondary or tertiary is taken into account by f.

Infrared spectroscopy of quasi-ideal binary liquid mixtures: The challenges of conventional chemometric regression.

We have recorded ATR-IR spectra of binary mixtures in the (quasi-)ideal systems Benzene-Toluene, Benzene-Carbon tetrachloride and Benzene-Cyclohexane and performed classical least squares, inverse least squares and principal component regression on the resulting spectra. In contrast to the general expectation, the spectra of ideal mixtures follow only roughly Beer's approximation, in particular stronger bands show shifts and increased intensities for intermediary compositions since the polarization of matter by light cannot be neglected. As a consequence, these conventional regression techniques lead to principle and unavoidable errors, even though some of the classical regression techniques are assumed to be able to cope with nonlinearities.

The Negative Solvatochromism of Reichardt's Dye B30 - A Complementary Study.

The UV/Vis spectra of a hypothetical negative solvatochromic dye in a solvent are theoretically calculated assuming the classical damped harmonic oscillator model and the Lorentz-Lorenz relation. For the simulations, the oscillator strength of the solvent was varied, while for the solute all oscillator parameters were kept constant. As a result, a simple change of the oscillator strength of the solute can explain the redshift and intensity increase of the UV/Vis band of the solute.

To generate a photonic nanojet outside a high refractive index microsphere illuminated by a Gaussian beam.

A non-resonant, concentrated, narrow beam of light emerging from an illuminated microlens is called a photonic nanojet (PNJ). According to currently prevailing opinion, microspheres and microcylinders are only able to generate a PNJ in their exterior when their refractive index ns (or refractive index contrast) is less than 2. In this Letter we demonstrate that a PNJ can emerge from a microsphere even when ns > 2: first by employing the laws of geometrical optics for a divergent light source; then, by using ray transfer matrix analysis, a mathematical condition for the Gaussian beam (GB) outside the high ns microsphere is derived.

Smart Error Sum Based on Hybrid Two-Trace Two-Dimensional (2T2D) Correlation Analysis.

Based on hybrid 2D correlation analysis, we recently derived and introduced a "smart error sum," a sophisticated loss function that can be used for solving nonlinear inverse problems like the determination of optical constants and oscillator parameters from a series of optical spectra in the infrared spectral region. The advantage of the smart error sum compared to the conventional sum of squared errors lies in its ability to marginalize multiplicative systematic errors such as, for example, reflectance values above unity in transflection spectra. This is enabled by a transformation, which allows fits to not exclusively focus on forcing fit spectra to agree with experimental spectra at every wavenumber point by all means, but also to take correlations such as spectral similarities and their changes with certain perturbations into account.

Detection of siloxane thin films on glass substrate using IR ratio-reflectance spectrum.

In case of thin films of siloxane obtained from different organo-silane derivatives (alkoxy and chloro) on soda lime silica glass substrates, IR-ATR and IR-SR could not detect the organic functional groups of the coating. This becomes even more problematic for the case of tetraethoxysilane (when fully hydrolyzed), the coating of which possesses the same functional groups as the glass substrate. In this work we propose to employ the so-called ratio-reflectance spectra in the v(Si-O) wavenumber region, where both glass and the siloxane coating give most prominent bands, important for the evaluation of the quality of coating formation and qualitative knowledge on its structure.

Infrared refraction spectroscopy - Kramers-Kronig analysis revisited.

Since about 60 years, it is possible to determine the set of optical constants from reflectance measurements by the Kramers-Kronig relations. Unfortunately, the potential of the method seems to be limited in practice by the need to extend measured data into unknown regions by extrapolation, which is prone to error and leads to deviations from the true values in the known region depending on the method of extension. With the advent of infrared refraction spectroscopy, which uses reflectance measurements at normal or near normal incidence, the development of a fast method to determine the complex index of refraction function reliably for these cases has become an even more interesting goal.

Beyond Beer's Law: Quasi-Ideal Binary Liquid Mixtures.

We have recorded attenuated total reflection infrared spectra of binary mixtures in the (quasi-)ideal systems benzene-toluene, benzene-carbon tetrachloride, and benzene-cyclohexane. We used two-dimensional correlation spectroscopy, principal component analysis, and multivariate curve resolution to analyze the data. The 2D correlation proves nonlinearities, also in spectral ranges with no obvious deviations from Beer's approximation.

Hybrid 2D Correlation-Based Loss Function for the Correction of Systematic Errors.

We present the derivation of a new kind of loss function from the symmetry rules of synchronous and asynchronous two-dimensional correlation maps. This loss function, which takes into account correlations that are based on causal relations among the members of a series of spectra, can be employed to solve non-linear inverse problems that are plagued by systematic multiplicative errors. This possibility results from the correlation-based loss function being practically insensitive to such systematic errors, which often arise in spectroscopy because sample spectra are usually ratioed against reference spectra.