The strong CO ligand vibrations of an octahedral complex, fac-[Re (CO)3(bpy)(CH3CN)]+, in acetonitrile are observed at 2040 and 1932 cm-1. Facial rhenium tricarbonyl systems offer very strong and isolated CO vibrations with the potential for interactions between these vibrations. This work first identifies the dominant ion-pair species using attenuated total reflection infrared (ATR-IR) absorption spectra on a dilution series and then determines the strength of these CO ligand vibrations (as isolated vibrations) with a combination of ATR-IR and etalon-based measurements that determine the absolute complex index of refraction of the solution. Finally, the etalon experiments are modeled to study the interaction between vibrations, which is a property not embedded in the solution's complex index of refraction. The ATR-IR spectra are accomplished on a dilution series as well as a larger set of spectra as these solutions evaporated. The A'(1) CO ligand band at 2040 cm-1 is fit with a sum of three Lorentzian functions characterizing the distribution of free, solvent-separated, and contact ion pairs of this octahedral complex vs concentration. The other CO ligand band at 1932 cm-1 is broader and complicated by the dynamics of vibrational interactions, the unresolved splitting of the A'(2) and A″ CO vibrations, and ion-pair speciation. The etalon transmission measurements vs angle were on a 0.029 M solution, and Rabi splittings of 19 and 38 cm-1 were observed for the A'(1) CO vibration and the unresolved A'(2) + A″ CO vibrations, respectively. The great strength of the CO ligand vibrations is evident despite the use of a dilute solution. Integrated band intensities are reported in comparison to hybrid density functional calculations for isolated vibrations. Then, the observed Rabi splittings are modeled to obtain the coupling strength of the CO ligand vibration with etalon cavity modes and with each other. In summary, this work develops a method to determine the concentration of these solutions from the ATR-IR spectrum, characterizes the ion-pairing, shows that the index of refraction is not constant in the IR spectral region of interest, and develops an interaction Hamiltonian that characterizes cavity-vibration and vibration-vibration coupling.

A new method is established using an etalon cavity to assist in the determination of the wavelength-dependent complex index of refraction of a solution throughout the mid-infrared range. The results are used to study the cavity-vibration polaritons of PF6- in acetonitrile. Mixed states are formed by placing solution inside a pair of parallel plate mirrors with a wavelength-scale spacing, i.e., within an etalon, such that there are cavity states that are angle-tuned into resonance with the strong P-F vibrations. The dominant ν3 vibrations of PF6- consist of nearly triply degenerate oscillations of the partial-positively charged phosphorous against antisymmetric concerted motions of different sets of fluorine atoms with partial negative charges. These vibrations are dominant even though the solute is 29 times less concentrated than the solvent on a molar basis. The first part of the paper describes the method of determining the complex index of refraction of the solution from a combination of etalon transmission maxima and the attenuated total reflection (ATR) absorption spectrum of the solution. The results are presented as an analytical function including a sum of 37 vibrational contributions. Absolute integrated isolated band intensities were determined to be 463 ± 4, 462 ± 7, and 266 ± 4 km/mol for the three ν3 PF6- vibrations at 841.4, 847.4, and 854.0 cm-1, respectively, which sum to 1191 ± 9 km/mol for the ν3 band. Then, the results are used to simulate the measured etalon transmission using the transfer matrix (TM) method with and without the ν3 target vibrations. The etalon transmission simulations reconstruct the position of cavity modes in the absence of target vibrations. They provide input data for the testing of simple quantum mechanical models for the interaction of vibrations with cavity modes and the interactions of vibrations with other vibrations within the molecule and between solute and solvent. The model shows that the nearly degenerate ν3 vibrations interact with each other with a vibration-vibration coupling of 33 ± 5 cm-1. This is comparable to the cavity-vibration coupling of 30.4 ± 2.9 cm-1 of the two strongest vibrations of PF6-.

Etalons are pairs of parallel plate mirrors with wavelength-scale spacing that exhibit cavity modes, giving transmission maxima (fringes) due to constructive interference. Infrared transmission measurements as a function of angle were used to determine the effective mass of etalon cavity modes using a gap filled with air and then liquid carbon tetrachloride. The air-filled etalon gives results in agreement with pure photon expectations established herein. Liquids with vibrations having strong infrared transition intensity (vibrational strong coupling mode) can strongly perturb the pattern of transmission resonances, creating mixed states of infrared cavity modes and molecular vibrations, i.e., cavity-vibration polaritons. The effective mass of one cavity-vibration polariton close to the strong vibration of carbon tetrachloride is 4.36 times heavier than the pure photon cavity mode expectation, i.e., the mass factor vs pure light. The mass factors are largest when closest to the strong vibrational frequency, and they converge to the one far away from the strong vibration. This work gives quantitative values of the effective mass of cavity-vibration polariton states and is a diagnostic for the mixing of vibrations with etalon transmission.

This work is the first report on nonzero molecular vibration-vibration coupling in an infrared cavity-vibration experiment. Vibration-vibration coupling strength is determined as a cavity mode of parallel spaced mirrors (etalon mode or fringe) is angle-tuned in the region between two vibrations of liquid acetonitrile which are Fermi coupled, namely, a CN stretch dominated vibration and a nearby combination band dominated by the symmetric CH3 bend and C-C stretch. All other infrared cavity-vibration work to date involving more than one vibration has used a value of zero for vibration-vibration coupling; however, this work starts with Fermi coupled vibrations and reveals that there are changes in the vibration-vibration coupling and cavity-vibration couplings as the cavity mode is angle-tuned between the interacting vibrations. The ability to change fundamental vibrational dynamics within a cavity is an exciting result which helps to build a foundation for understanding molecular vibrational dynamics in parallel plate etalon cavities.

A Rabi splitting of 43.0 ± 1.0 cm-1 (95% conf.) was determined for the interaction of the CD3 deformation, the strongest fundamental vibration of the liquid CD3C≡N molecule and fringe modes of a parallel-plate Fabry-Pérot cavity containing this liquid. Note that vibration-cavity polaritons are also called dressed states, hybrid or mixed states. Since the experimental configuration has many orders of magnitude more vibrational oscillators than photons, vibrational oscillators not in dressed states far outnumber those in the dressed states. This work is distinguished from related vibration-cavity work by a method to extract the position, width, phase, and intensity of bulk vibrational signals including reconstruction of the position of the fringe without vibrational contributions. It reveals how the bulk vibrational oscillators are changed by interaction within the cavity even though they are not in dressed states. Although the dressed states are obvious targets for manipulation of chemical response, it is interesting to consider whether the lesser but more prevalent changes of the bulk vibrations can also be used to change the chemical response.

Rabi splittings are now being routinely measured for condensed phase vibrations interacting with the modes of a parallel plate etalon of wavelength-scale spacing by means of Fourier Transform Infrared (FTIR) spectrometers. Considering that the width of an etalon fringe is a critical parameter in experiments of cavity-vibration interactions, it is noteworthy that the fringes are strongly affected by non-ideal conditions such as the angular spread of the FTIR beam and/or etalon misalignment. This work characterizes how parallel plate etalons are affected by angular spread in our FTIR and presents a method to reconstruct fringes that are strongly affected by vibrations by using those unaffected by strong vibrations.

This work characterizes collections of infrared spectra of individual dust particles of approximate to 4 mu m size that were obtained from three very different environments: our lab air, a home air filter, and the 11 September 2001 World Trade Center event. Particle collection was done either directly from the air or by placing dust powder from various samples directly on the plasmonic mesh with 5 mu m square holes as air is pumped through the mesh. This arrangement enables the recording of scatter-free infrared absorption spectra of individual particles of size comparable to the probing wavelengths whose vibrational signatures are otherwise dominated by scattering and dispersive line shape distortions. The spectra are sensitive to the amounts of various infrared active components and analysis using a Mie-Bruggeman model for mixed composition particles provides volume fractions of the components. Inhalation of dust particles of approximate to 4 mu m size has significant health consequences as these are among the largest inhaled into people's lungs. The chemical composition of approximate to 4 mu m respirable particles is of great interest from health, atmospheric, and environmental perspectives as different environments may pose different hazards and spectroscopic challenges.

A Mie-Bruggeman model is used to predict the shape and orientation-averaged infrared extinction and absorption spectra of a Saharan dust sample of mixed composition and size. The common minerals of atmospheric dust samples, clays in this case, have strong infrared transitions which match the particle size and probing wavelengths giving rise to interesting lineshape distortions. These distortions may need to be considered for quantitative analysis of infrared spectra measurements of atmospheric dust samples.

Plasmonically enhanced effects on a self-assembled, hexagonal array layer of ~4-nm silver nanoparticles are analyzed using three-dimensional finite-difference time-domain (3D FDTD) simulations and compared against experimentally measured extinction spectra. The effect of particle size, lattice spacing, and lack of monodispersity of the hexagonal array of silver nanoparticles on the extinction resonance was investigated to help determine optimal design specifications for efficient organic solar power harvesting.

Infrared (IR) imaging spectroscopy of human liver tissue slices has been used to identify and characterize liver metastasis of colorectal origin which was surgically removed from a consenting patient and frozen without formalin fixation or dehydration procedures, so that lipids and water remain in the tissues. First, a k-means clustering analysis, using metrics from the IR spectra, identified groups within the image. The groups were identified as tumor or nontumor regions by comparing to an H&E stain of the same sample after IR imaging. Then, calibrant IR spectra of protein, several fats, glycogen, and polyvinyl alcohol were isolated by differencing spectra from different regions or groups in the image space. Finally, inner products (or scores) of the IR spectra at each pixel in the image with each of the various calibrants were calculated showing how the calibrant molecules vary in tumor and nontumor regions. In this particular case, glycogen and protein changes enable separation of tumor and nontumor regions as shown with a contour plot of the glycogen scores versus the protein scores.

The Coe Group has used plasmonic metal films with arrays of microholes to capture particles and record scatter-free infrared absorption spectra of individual dust particles of a specific size and narrow size distribution using imaging infrared Fourier transform microscopy. The spectra are scatter-free in spite of the fact that these particles are smaller than the probing wavelengths of light. Dust particles of ~4 m size have been collected from different environments, including data from our laboratory air, a household filter, the World Trade Center 9/11/2001 event, and the International Space Station. Particles of this size are among the largest that are inhaled into people’s lungs, so there is much interest in the chemical composition of these particles considering that increasing particulate concentrations are known to be correlated with deterioration of human health. In addition to samples from various environments, the dust library now includes the spectra of single particles of calibrants, i.e. pure components known to be in the dust which enables the development of quantitative analytical models for composition.

Infrared (IR) spectra from 1200 to 1800 cm(-1) of the pure α-helix and β-sheet secondary structures have been extracted using a covariant least-squares procedure which relates a library of 40 infrared (IR) solution protein spectra from the work of Dong, Carpenter, and Caughey and amino acid fractions of the proteins based on assignments by STRIDE (secondary structure identification) of Eisenhaber and Argos. The excitonic splitting of the β-sheet structures is determined for this library of solution proteins. The method is extended to find a set of spectral basis functions that analyze IR spectra of protein samples for α-helix and β-sheet content. A rigorous error analysis including covariance, the correlations between the input library spectra, was used to justify the results and avoid less meaningful results. The utility of the results on α-helix and β-sheet regions is demonstrated by detecting protein changes due to cancer in imaging Fourier transform IR (FTIR) spectra of liver tissue slices. This work ends with a method to extract IR spectra of less prominent torsional angle distributions.

The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (n<m)). Bulk values of these thermodynamic potentials were obtained using a previously demonstrated robust method based on semi-empirical PM3 calculations and an extrapolated cluster approach. Those values were used to study the relationship between the thermodynamic potentials and the diameter of the nanotube. Results of this study led to the proposal of a single equation for the thermodynamical potential of [Formula: see text] or [Formula: see text] (assembly of nanotubes from atoms) versus the chiral vector indexes n and m for any given nanotube. The equations show a good level of accuracy in predicting thermodynamic potentials for practical applications.

Infrared (IR) imaging spectroscopy of human liver tissue slices has been used to identify and characterize a liver metastasis of breast origin (mucinous carcinoma) which was surgically removed from a consenting patient and frozen without formalin fixation or dehydration procedures, so that lipids and water remain in the tissues. Previously, a set of IR metrics was determined for tumors in fixation-free liver tissues facilitating a k-means cluster analysis differentiating tumor from nontumor. Different and more in depth aspects of these results are examined in this work including three metric color imaging, differencing for lipid identification, and a new technique to simultaneously fit band lineshapes and their 2nd derivatives in order to better characterize protein changes.

A plasmonic metal film with a subwavelength hole array (a mesh) is used to capture an individual subwavelength particle, like a single yeast cell or airborne dust particle, and an imaging infrared (IR) microscope, records a scatterfree, IR absorption spectrum of the particle. Individual spectra of wavelength scale particles usually suffer from large scattering effects. This paper starts by demonstrating the plasmonic nature of the mesh in the infrared, proceeds to how this special form of light (surface plasmon polariton mediated transmission resonance) leads to scatter-free IR absorption spectra of individual, subwavelength particles, and ends with work on yeast cells and dust particles from our laboratory air and a household filter.

The high fractional open area of metal thin film coatings, with two dimensional, hexagonally ordered, close packed arrays of holes, makes them of interest for the incorporation of plasmonic effects into a variety of optical devices. Gold films with hexagonal patterns of circular holes have been created on ZnSe infrared windows. The films have 2.50 μm diameter holes and a hexagonal lattice parameter of 3.06 μm which places the primary transmission resonances of the ZnSe/gold interface at ~1,400 cm−1 (7.14 μm) and that of the air/gold interface at ~3,800 cm−1 (2.63 μm). This geometry produces useful transmission across the whole traditional mid-infrared range. The dispersion of these resonances has been measured by changing the angle of incident light. The data is modeled with explicit momentum matching equations in two different, high symmetry geometries, allowing the effective index of refraction to vary with wavelength. The response of these resonances to the addition of an acetaldehyde coating is described.

Beyond our own interest in airborne particulate matter, the prediction of extinction and absorption spectra of single particles of mixed composition has wide use in astronomy, geology, atmospheric sciences, and nanotechnology. Single particle spectra present different challenges than traditional spectroscopic approaches. To quantify the amount of a material in a bulk sample (molecules in solution or the gas phase), one might employ the Beer-Lambert law assuming a simple slab-type assay geometry and averaging over orientation, whereas with single particles one might have a specific orientation and require a nonlinear, Mie-like particle theory. The complicating single particle issues include: strong and broad scattering at wavelengths similar to the particle size, phonon lineshape phase shifting, particle shape effects, distortion of transition lineshapes by strong vibrational bands, bi- and trirefringence, crystal orientation effects including dispersion, and composition mixtures. This work uses a combination of three-dimensional finite difference time domain (3D-FDTD) calculations and experimental infrared spectra on single, crystalline quartz particles to illustrate some of the challenges - in particular the distortion of lineshapes by strong phonons that lie within a range of strong scattering. It turns out that many mineral dust components in the inhalable size range have strong phonons. A Mie-Bruggeman model for single particle spectra is presented to isolate the effects of strong phonons on lineshapes which has utility for analysing the spectra of single, mixed-composition particles. This model will ultimately enable the determination of volume fractions of components in single particles that are mixtures of many materials with strong phonons, as are the dust particles breathed into people's lungs.

A Mie-Bruggeman spectral model is presented which predicts the orientationally averaged, infrared spectra of individual mixed-composition particles or the average spectrum of collections of such particles. The model uses parameters extracted from sets of individual particle spectra of pure materials known to be in subject mixtures. The spectra of both calibrants and subject particles were recorded by trapping size-selected particles in the holes of plasmonic metal mesh. Calibrating data is presented for quartz, calcite, dolomite, three clays, gypsum, polyethylene, and living organic material (yeast cells). The individual particle spectra of these calibrants are averaged to account for crystal orientation effects, fit by a Mie theory model, and tabulated herein as dielectric functions of each component. The component dielectric functions are combined in this model with Bruggeman effective medium theory producing a spectral prediction for mixed-composition particles. The Mie-Bruggeman model was used to analyze the composition of dust from our lab air [K. E. Cilwa et al. J. Phys. Chem. C 2011, 115, 16910] based on the average spectrum of the dust particles. The model does a reasonable job of characterizing the dust in our laboratory air exhibiting promise for future applications. This work presents the model and illustrates potential; however, much more work will be required before its accuracy as a quantitative analytical method is established.

Infrared (IR) spectroscopic imaging of human liver tissue slices has been used to identify and characterize liver tumors. Liver tissue, containing a liver metastasis of breast origin (mucinous carcinoma), was surgically removed from a consenting patient and frozen without formalin fixation or dehydration procedures, so that lipids and water remained in the tissues. A set of IR metrics (ratios of various IR peaks) was determined for tumors in fixation-free liver tissues. K-means cluster analysis was used to tell tumor from nontumor. In this case, there was a large reduction in lipid content upon going from nontumor to tumor tissue, and a well-resolved IR spectrum of nontumor liver lipid was obtained and analyzed. These IR metrics may someday guide work on IR spectroscopic diagnostics on patients in the operating room. This work also suggests utility for these methods beyond the identification of liver tumors, perhaps in the study of liver lipids.