Sum frequency generation as a proxy for ellipsometry: Not just a phase.

Infrared refractive indices of organic materials are typically resolved through IR ellipsometry. This technique takes advantage of optical interference effects to solve the optical constants. These are the same effects that complicate the analysis of coherent spectroscopy experiments on thin films. Vibrational sum frequency generation is an interface-specific coherent spectroscopy that requires spectral modeling to account for optical interference effects to uncover interfacial molecular responses. Here, we explore the possibility of leveraging incident beam geometries and sample thicknesses to simultaneously obtain the molecular responses and refractive indices. Globally fitting a higher number of spectra with a single set of refractive indices increases the fidelity of the fitted parameters. Finally, we test our method on samples with a range of thicknesses and compare the results to those obtained by IR ellipsometry.

Ruthenium hydrides encapsulated in sol-gel glasses exhibit new ultrafast vibrational dynamics.

Vibrational dynamics were measured by IR pump-probe spectroscopy and two-dimensional IR spectroscopy for triruthenium dodecacarbonyl and the undecacarbonyl hydride that forms when it is encapsulated in an alumina sol-gel glass. For comparison, a triruthenium undecacarbonyl hydride salt was also synthesized and studied in neat solution to identify the potential influence of the confined solvent environment on the dynamics experienced by carbon monoxide ligands. The vibrational lifetime was found to be significantly decreased for both hydride species relative to the dodecacarbonyl compound. Conversely, spectral diffusion of the CO vibrations was measured to be faster for the parent compound. The most significant dynamic changes occurred upon transformation from the starting compound to the hydride, while only minor differences were observed between the dynamics of the freely dissolved and sol-gel encapsulated hydrides. The results suggest that the structural change to the hydride has the largest impact on the dynamics and that its improved catalytic properties likely do not originate from confined solvent effects.

The role of ultrafast structural dynamics with physical and chemical changes in polydimethylsiloxane thin films by two-dimensional IR spectroscopy.

Fourier transform infrared (FTIR) and two-dimensional IR (2D-IR) spectroscopies were applied to polydimethylsiloxane (PDMS) cross-linked elastomer films. The vibrational probe for the systems studied was a silicon hydride mode that was covalently bound to the polymer chains. The structure and dynamics reported by this mode were measured in response to a wide range of chemical and physical perturbations, including elevated curing temperature, increased curing agent concentration, mechanical compression, and cooling to near the glass transition temperature. The FTIR spectra were found to be relatively insensitive to all of these perturbations, and 2D-IR spectroscopy revealed that this was due to the overwhelming influence of heterogeneity on the spectral line shape. Surprisingly, the deconvoluted spectral line shapes showed that there were only slight differences in the heterogeneous and homogeneous dynamics even with the drastic macroscopic changes occurring in different systems. In the context of modeling polymer behavior, the results confirm that dynamics on the ultrafast time scale need not be included to properly model PDMS elasticity.

Simplified sum frequency generation using a narrow free-spectral-range etalon.

We report the implementation of a narrow free-spectral-range Fabry-Perot etalon for multiplex vibrational sum frequency generation (VSFG) spectroscopy. Moreover, we demonstrate the use of the etalon reflection to simultaneously generate a broadband infrared pulse, which enables a multiplex VSFG spectrometer using a total of 0.58 W. VSFG spectra with and without a nonresonant-suppressed background were simultaneously collected utilizing time asymmetry in the upconverting pulse. Two examples are demonstrated in which spectral perturbations can be induced by the time-asymmetric pulse even without nonresonant suppression.

Influence of Solvent Swelling on Ultrafast Structural Dynamics in Polydimethylsiloxane Thin Films by Two-Dimensional IR Spectroscopy.

Fourier transform infrared and two-dimensional IR (2D-IR) spectroscopies were applied to polydimethylsiloxane (PDMS) cross-linked elastomer and a siloxane oligomer without solvent and swollen or dissolved in various solvents. The silicon hydride, which is covalently bound to the polymer chains, was the vibrational probe for the systems studied. There is almost an absence of vibrational solvatochromism in these systems. Frequency-frequency correlation functions obtained by 2D-IR spectroscopy show that the insensitivity of the FTIR spectra is due to overwhelming heterogeneity. However, the homogeneous contribution to the FTIR spectrum is smaller for the elastomer than the oligomer showing that the cross-linking process restricts the frequency fluctuations that are experienced by the hydride mode. The silicon hydride mode in a cross-linked, solvent-free PDMS film also exhibits spectral diffusion that must be due to polymer structural motions on the ultrafast time scale that are active above the glass transition temperature. Once solvents penetrate and swell the elastomer, the polymer likely continues to experience these polymer structural motions. However, we find that the vibrational dynamics are characteristic of the infiltrating solvents, showing that at least some fraction of the measured dynamics originate in solvent motions.

Enhanced vibrational solvatochromism and spectral diffusion by electron rich substituents on small molecule silanes.

Fourier transform infrared and two-dimensional IR (2D-IR) spectroscopies were applied to two different silanes in three different solvents. The selected solutes exhibit different degrees of vibrational solvatochromism for the Si-H vibration. Density functional theory calculations confirm that this difference in sensitivity is the result of higher mode polarization with more electron withdrawing ligands. This mode sensitivity also affects the extent of spectral diffusion experienced by the silane vibration, offering a potential route to simultaneously optimize the sensitivity of vibrational probes in both steady-state and time-resolved measurements. Frequency-frequency correlation functions obtained by 2D-IR show that both solutes experience dynamics on similar time scales and are consistent with a picture in which weakly interacting solvents produce faster, more homogeneous fluctuations. Molecular dynamics simulations confirm that the frequency-frequency correlation function obtained by 2D-IR is sensitive to the presence of hydrogen bonding dynamics in the surrounding solvation shell.

Frequency comb SFG: a new approach to multiplex detection.

Determination of molecular orientation at interfaces by vibrational sum frequency generation spectroscopy (VSFG) requires measurements using at least two different polarization combinations of the incoming visible, IR, and generated SFG beams. We present a new method for the simultaneous collection of different VSFG polarization outputs by use of a modified 4f pulseshaper to create a simple frequency comb. Via the frequency comb, two visible pulses are separated spectrally but aligned in space and time to interact at the sample with mixed polarization IR light. This produces two different VSFG outputs that are separated by their frequencies at the monochromator rather than their polarizations. Spectra were collected from organic thin films with different polarization combinations to show the reliability of the method. The results show that the optical arrangement is immune to fluctuations in laser power, beam pointing, and IR spectral shape.

Simple fully reflective method of scatter reduction in 2D-IR spectroscopy.

A fully reflective two-dimensional IR (2D-IR) setup is described that enables efficient cancellation of scattered light from multiple pulses in the phase-matched direction. The local oscillator pulse and the pulse that stimulates the vibrational echo signal are synchronously modulated (or fibrillated) in time maintaining their phase relationships with the echo wavepacket. The modification is cost-effective and can be easily implemented on existing 2D-IR instruments, and it avoids the addition of dispersive elements into the beam paths. The fibrillation results in a decrease of waiting-time resolution of only tens of femtoseconds and has no impact on the spectral lineshape, making it a general improvement for 2D-IR spectrometers even for weakly or non-scattering samples.

Experimental evidence for an optical interference model for vibrational sum frequency generation on multilayer organic thin film systems. I. Electric dipole approximation.

In the field of vibrational sum frequency generation spectroscopy (VSFG) applied to organic thin film systems, a significant challenge to data analysis is in the accurate description of optical interference effects. Herein, we provide experimental evidence that a model recently developed in our lab provides an accurate description of this phenomenon. We studied the organic small molecule N,N'-dioctyl-3,4,9,10-perylenedicarboximide vapor deposited as a thickness gradient on silicon wafer substrates with two oxide thicknesses and two surface preps. VSFG data were obtained using the ssp and the sps polarization combinations in the imide carbonyl stretching region as a function of organic thickness. In this first of two reports, the data are modeled and interpreted within the ubiquitous electric dipole approximation for VSFG. The intrinsic sample responses are parameterized during the fitting routines while optical interference effects are simply calculated from the model using known refractive indices, thin film thicknesses, and beam angles. The results indicate that the thin film model provides a good description of optical interferences, indicating that interfacial terms are significant. Inconsistencies between the fitting results within the bounds of the electric dipole response motivate deliberation for additional effects to be considered in the second report.

Experimental evidence for an optical interference model for vibrational sum frequency generation on multilayer organic thin film systems. II. Consideration for higher order terms.

The generalized optical interference model for interfacial contributions to vibrational sum frequency generation (VSFG) spectroscopic signals from organic thin film systems is extended to include a description of optical interferences contained in the thin film bulk response. This is based on electric quadrupolar interactions with the input fields and includes a discussion on possible contribution from the electric quadrupolar polarization. VSFG data from the first of this two part report are analyzed and include effects from higher order responses, for both bulk and higher order interfacial terms. The results indicate that although it is capable of capturing many of the data features, the electric dipole treatment is likely not a complete description of the VSFG intensity data from this system. An analysis based on the signs of the resulting response amplitudes is used to deduce the relative magnitude of the electric dipole and higher order interfacial terms. It is found that the buried interface is closer to satisfying the electric dipole approximation, consistent with smaller field gradients due to closer index matching between the organic thin film and substrate relative to air. The procedure outlined in this work allows for the difficult task of deducing a physical picture of average molecular orientation at the buried interface of a multilayer organic thin film system while including higher order effects.

Correlating solvent dynamics and chemical reaction rates using binary solvent mixtures and two-dimensional infrared spectroscopy.

Two-dimensional infrared (2D-IR) spectroscopy was performed on Vaska's complex (VC) and its oxygen adduct (V C-O2) in binary solvent mixtures of chloroform or benzyl alcohol in d6-benzene. The second order rate constants for oxygenation were also measured in these solvent mixtures. The rate constant in chloroform mixtures is linear with mole fraction within the error of the measurements but changes nonlinearly in benzyl alcohol mixtures, displaying a preference for the alcohol over benzene. The rate constants were compared with FTIR spectra of the carbonyl ligand and the frequency-frequency correlation function of this mode determined by 2D-IR. The line shape broadening mechanisms of the linear spectra of the CO bound to VC and V C-O2 are similar to those previously reported for V C-I2. There is a particularly strong correlation between rate constants and homogeneous linewidths of the carbonyl vibration on the V C-O2 product state. Concurrently, the FTIR spectra and spectral diffusion observed by 2D-IR corroborate an increase in solvent heterogeneity around the product. We interpret these results in the context of the potential role of solvent dynamics in facilitating chemical reactivity.

Solvent-mediated vibrational energy relaxation from Vaska's complex adducts in binary solvent mixtures.

A vibrational pump-probe and FTIR study was performed on two different adducts of Vaska's complex in two different sets of binary solvent mixtures. The carbonyl vibrational mode in the oxygen adduct exhibits solvatochromic shifts of ~10 cm(-1) in either benzyl alcohol or chloroform relative to benzene-d6, whereas this vibration is nearly unchanged for the iodine adduct for the same three solvents. The width and center frequency of the carbonyl stretch for each adduct are compared to its vibrational lifetime in binary mixtures of benzene-d6 with either benzyl alcohol or chloroform. In neat solvents, the trends in line width, frequency, and vibrational lifetime are consistent for the two adducts, but complex relationships emerge when the trends in each property are compared as a function of mixed solvent composition. ν(CO) is more sensitive to the solvation environment around the trans ligand, whereas the line width and lifetime depend on the environment around the CO group itself. The carbonyl frequency and width vary nonlinearly across the two binary solvent series, indicating preferential solvation. In contrast, the vibrational lifetime changes linearly with solvent composition and is correlated with the mole fraction of chloroform but anticorrelated with the mole fraction of benzyl alcohol. The results are explained by differences in the densities of solvent modes that affect intermolecular relaxation of the carbonyl mode.

Simulated vibrational sum frequency generation from a multilayer thin film system with two active interfaces.

In the field of surface-specific vibrational sum frequency generation spectroscopy (VSFG) on organic thin films, optical interferences combined with the two-interface problem presents a challenge in terms of qualitative assessment of the data and quantitative modeling. The difficulty is amplified when considering systems comprised of more than a single material thin film layer. Recently, in our lab we have developed a generalized model that describes thin film interference in interface-specific nonlinear optical spectroscopies from arbitrary multilayer systems. Here, we apply the model to simulate VSFG spectra from the simplest multilayer: a system of two thin films, one of which is an organic small molecule and the other is a dielectric layer on a semiconductor substrate system where we idealize that the organic interfaces are equally VSFG active. Specifically, we consider the molecule N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) deposited on a silicon wafer with a thermally grown oxide dielectric. We present results for the four polarization experiments that sample the nonzero nonlinear susceptibility elements of macroscopically centrosymmetric materials (ssp, sps, pss, and ppp) and in two mIR frequency windows (the imide carbonyl stretches around 1680 cm(-1) and the alkyl stretches around 2900 cm(-1)) as a function of both thin film thicknesses with fixed input beam angles. We use frequency dependent refractive indices for all materials. The goal is to illustrate some of the intricacies contained in the intensity data of such systems. Of particular interest is the effect of the relative polar orientation of modes at the interfaces and the possibility of designing a system where the collected signal is exclusively attributable to a single interface. Our calculations indicate that in order to unambiguously identify the relative polar orientation one must experimentally vary an additional system parameter such as thin film thickness or input beam angle and for quantitative modeling one cannot ignore either interfacial contribution. The results show that proper modeling of thin film interference effects is essential for accurate data analysis and should include the frequency dependent refractive indices, especially for modes with larger mIR absorption cross sections, even when absorptive losses are small.

Polarization-multiplexed vibrational sum frequency generation for comprehensive simultaneous characterization of interfaces.

We describe a novel three-pulse experimental arrangement for the simultaneous generation and subsequent resolution of all four electric-dipole allowed vibrational sum frequency generation polarization combinations. For noncentrosymmetric and achiral systems, this represents full characterization of all symmetry-allowed elements of the second-order susceptibility, providing a comprehensive intensity level assessment of the system under study. By measuring all relevant signals simultaneously, this approach enables assessment of molecular orientation and structure in dynamic, temporally evolving systems that were previously inaccessible by means of sequentially scanned acquisition of the individual tensor elements.

Vibrational solvatochromism in Vaska's complex adducts.

The vibrational solvatochromism of bis(triphenylphosphine) iridium(I) carbonyl chloride (Vaska's complex, VC) was investigated by FTIR spectroscopy. The carbonyl stretching frequency (ν(CO)) was measured in 16 different organic solvents with a wide range of Lewis acidities for VC and its dioxygen (VC-O(2)), hydride (VC-H(2)), iodide (VC-I(2)), bromide (VC-Br(2)), and sulfide (VC-S(X)) adducts. The ν(CO) of the VC-O(2) complex was sensitive to the solvent electrophilicity, whereas minimal correlation was found for VC and the other adducts. The stretching frequency of the trans-O(2) ligand on VC-O(2) was measured to be anticorrelated with ν(CO), supporting a model in which this ligand indirectly affects the carbonyl frequency by modulating the extent of metal-to-CO back-bonding. The ν(CO) values obtained from DFT calculations on VC adducts with solvent continua and explicit hydrogen bonds were used to aid the interpretations of the experimental results. The O(2) ligand is more susceptible to stronger specific solvent interactions and it binds in a fundamentally different mode from the monatomic ligands, providing a more direct communication channel with those metal d-orbitals that have the appropriate symmetry to back-bond into the carbonyl π*-orbital.

Surface chemistry and annealing-driven interfacial changes in organic semiconducting thin films on silica surfaces.

Vibrational sum frequency generation (VSFG) spectroscopy was used in conjunction with steady-state IR spectroscopy, atomic force microscopy (AFM), and spectroscopic ellipsometry to characterize organic semiconductor thin films that were vapor deposited on silica- and trimethoxy(octadecyl)silane (ODTMS)-functionalized silica surfaces. The growth of perylene derivative N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C(8)) was found to proceed differently on simple glass slides relative to that of native oxide on silicon and fused quartz slides. VSFG was applied to these samples to isolate structural changes that occurred specifically at the buried interface between the organic semiconductor and the silica dielectric upon thermal annealing. A model was introduced to globally fit the imide carbonyl symmetric and asymmetric interfacial spectra that included contributions from both inner and outer interfaces. The fits to the VSFG data and AFM topographic images revealed significant reordering at the outer interface on all substrates upon thermal annealing. Within the model, the spectroscopic data reported that the inner interfacial PTCDI-C(8) monolayer reoriented to a more reclined phase on bare substrates after annealing but remained essentially unchanged on ODTMS monolayers. Electrical characterization of PTCDI-C(8) field-effect transistors indicated that electron mobilities were higher on bare substrate devices but could be improved by a factor of 2 on both surface types by thermal annealing. The mobility effects were attributed to the annealing-driven coalescence of PTCDI-C(8) grain boundaries. Consistent with previous structural reports, the molecular rearrangements of the first monolayer of PTCDI-C(8) on bare substrates that were reported by VSFG spectroscopy had a noticeable impact on the device performance.

Ultrafast Dynamics Experienced by Carbon Dioxide Diffusing through Polymer Matrices.

Fourier transform infrared, pump-probe polarization anisotropy, and two-dimensional infrared spectroscopies were used to study the steady-state and time-dependent behavior of carbon dioxide dissolved in three different polymer systems. Gas reorientation dynamics in poly(methyl methacrylate), poly(methyl acrylate), and poly(dimethylsiloxane) were sensitive to the nature of chemical interactions between the gas and polymer, as well as whether the polymer was in a glassy or rubbery phase. The homogeneous dynamics experienced by the asymmetric stretching vibration were found to be fastest for rubbery polymers with weak, nonspecific gas-polymer interactions. Spectral diffusion was absent for the carbon dioxide vibrational mode in glassy poly(methyl methacrylate) but was activated for the chemically similar but rubbery poly(methyl acrylate). The vibrational dynamics are shown to have a direct correlation with the diffusivity of carbon dioxide through the polymer matrices.

Spectroscopic Study of Sol-Gel Entrapped Triruthenium Dodecacarbonyl Catalyst Reveals Hydride Formation.

Triruthenium dodecacarbonyl exhibits increased catalytic activity toward hydrogenation reactions when encapsulated in alumina sol-gels. In this study, we demonstrate structural and electronic changes induced by the encapsulation process. Fourier transform infrared (FTIR) spectroscopy reveals that the carbonyl vibrational modes dramatically red shift during aging in the sol-gel glass. These shifts are attributed to the formation of the metal hydride: [HRu3(CO)11]-. A comparison to the FTIR spectrum of synthesized [NEt4][HRu3(CO)11] confirms this assignment. XPS studies show that the Ru 3d5/2 peak of [HRu3(CO)11]- also shifts to lower binding energy, consistent with an increased electron density on the Ru nuclei compared to Ru3(CO)12 and confirmed by density functional calculations. This study should open the door to further investigations into the hydride's role in the previously observed catalytic activity. To the best of our knowledge, this is the first study to identify the presence of [HRu3(CO)11]- in the alumina sol-gel.

Cytochrome c552 mutants: structure and dynamics at the active site probed by multidimensional NMR and vibration echo spectroscopy.

Spectrally resolved infrared stimulated vibrational echo experiments are used to measure the vibrational dephasing of a CO ligand bound to the heme cofactor in two mutated forms of the cytochrome c552 from Hydrogenobacter thermophilus. The first mutant (Ht-M61A) is characterized by a single mutation of Met61 to an Ala (Ht-M61A), while the second variant is doubly modified to have Gln64 replaced by an Asn in addition to the M61A mutation (Ht-M61A/Q64N). Multidimensional NMR experiments determined that the geometry of residue 64 in the two mutants is consistent with a non-hydrogen-bonding and hydrogen-bonding interaction with the CO ligand for Ht-M61A and Ht-M61A/Q64N, respectively. The vibrational echo experiments reveal that the shortest time scale vibrational dephasing of the CO is faster in the Ht-M61A/Q64N mutant than that in Ht-M61A. Longer time scale dynamics, measured as spectral diffusion, are unchanged by the Q64N modification. Frequency-frequency correlation functions (FFCFs) of the CO are extracted from the vibrational echo data to confirm that the dynamical difference induced by the Q64N mutation is primarily an increase in the fast (hundreds of femtoseconds) frequency fluctuations, while the slower (tens of picoseconds) dynamics are nearly unaffected. We conclude that the faster dynamics in Ht-M61A/Q64N are due to the location of Asn64, which is a hydrogen bond donor, above the heme-bound CO. A similar difference in CO ligand dynamics has been observed in the comparison of the CO derivative of myoglobin (MbCO) and its H64V variant, which is caused by the difference in axial residue interactions with the CO ligand. The results suggest a general trend for rapid ligand vibrational dynamics in the presence of a hydrogen bond donor.