Category: 2018

Quantifying conformations of ester vibrational probes with hydrogen-bond-induced Fermi resonances

Solvatochromic shifts of local vibrational probes report on the strength of the surrounding electric fields and the probe’s hydrogen bonding status. Stretching vibrational mode of the ester carbonyl group is a popular solvatochromic reporter used in the studies of peptides and proteins. Small molecules, used to calibrate the response of the vibrational probes, sometimes involve Fermi resonances (FRs) induced by inter-molecular interactions. In the present work, we focus on the scenario where FR does not appear in the infrared spectrum of the ester carbonyl stretching mode in aprotic solvents; however, it is intensified when a hydrogen bond with the reporter is established. When two molecules form hydrogen bonds to the same carbonyl oxygen atom, FR leads to strong hybridization of the involved modes and splitting of the absorption peak. Spectral overlap between the Fermi doublets associated with singly and doubly hydrogen-bonded carbonyl groups significantly complicates quantifying different hydrogen-bonded conformations. We employed a combination of linear and third-order (2DIR) infrared spectroscopy with chemometrics analysis to reveal the individual line shapes and to estimate the occupations of the hydrogen-bonded conformations in methyl acetate, a model small molecule. We identified a hydrogen-bond-induced FR in complexes of methyl acetate with alcohols and water and found that FR is lifted in larger molecules used for control experiments—cholesteryl stearate and methyl cyanoacetate. Applying this methodology to analyze acetonitrile-water solutions revealed that when dissolved in neat water, methyl acetate occupies a single hydrogen-bonding conformation, which is in contrast to the conclusions of previous studies. Our approach can be generally used when FRs prevent direct quantification of the hydrogen bonding status of the vibrational probe.
Authors: Anup Ghosh, Bar Cohn, Amit K Prasad, Lev Chuntonov

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Two-Dimensional Infrared Spectroscopy with Local Plasmonic Fields of a Trimer Gap-Antenna Array

Half-wavelength plasmonic antennas tuned to resonance with molecular vibrational excitations have been demonstrated to enhance 2DIR signals by multiple orders of magnitude. We design doubly degenerate in-plane plasmonic normal modes of the symmetric trimer gap-antenna, which have orthogonal dipole moments excited by light of the appropriate polarization, to localize the enhanced field into the antenna’s gap. Vibrational excitations serve as sensitive probes of the plasmonic fields. 2DIR spectroscopy of thin molecular films indicates that molecules emitting enhanced signals experience an electric field with a direction independent of the excitation laser pulse polarization. Our results illustrate the trade-off between the large signal amplification in molecules close to the antenna surface by resonant plasmons, where the direction of the enhanced fields follows metal surface boundary conditions, and the associated limitations for the polarization-selective spectroscopy. The ultrafast quantum dynamics reported by the enhanced signals is not affected by its interaction with plasmonic excitation.
Authors: Bar Cohn, Ben Engelman, Adi Goldner, Lev Chuntonov

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Artificial plasmonic molecules and their interaction with real molecules

Plasmonic molecules are small assemblies of nanosized metal particles. Interactions between the particles modify their optical properties and make them attractive for multiple applications in spectroscopy and sensing. In this review, we focus on basic properties rather than on applications. Plasmonic molecules can be created using either nanofabrication methods or self-assembly techniques in solution. The interaction of plasmonic molecules with light leads to excitations that are classified using the concept of normal modes. The simplest plasmonic molecule is a dimer of particles, and its lowest energy excitation takes the form of a symmetric dipolar mode. More complex excitations take place when a larger number of particles is involved. The gaps between particles in a plasmonic molecule form hotspots in which the electromagnetic field is concentrated. Introducing molecules into these hotspots is the basis of a vast spectrum of enhanced spectroscopies, from surface-enhanced Raman scattering to surface-enhanced fluorescence and others. We show in this review how these spectroscopic methods can be used to characterize the fields around plasmonic molecules. Furthermore, the strong fields can be used to drive new phenomena, from plasmon-induced chemical reactions to strong coupling of quantum emitters with the plasmonic fields. We systematically discuss these phenomena, introducing in each case the theoretical basis as well as recent experimental realizations.
Authors: Gilad Haran, Lev Chuntonov

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Radiative Enhancement of Linear and Third-Order Vibrational Excitations by an Array of Infrared Plasmonic Antennas

Infrared gold antennas localize enhanced near fields close to the metal surface, when excited at the frequency of their plasmon resonance, and amplify vibrational signals from the nearby molecules. We study the dependence of the signal enhancement on the thickness of a polymer film containing vibrational chromophores, deposited on the antenna array, using linear (FTIR) and third-order femtosecond vibrational spectroscopy (transient absorption and 2DIR). Our results show that for a film thickness beyond only a few nanometers the near-field interaction is not sufficient to account for the magnitude of the observed signal, which nevertheless has a clear Fano line shape, suggesting a radiative origin of the molecule–plasmon interaction. The mutual radiative damping of plasmonic and molecular transitions leads to the spectroscopic signal of a molecular vibrational excitation to be enhanced by up to a factor of 50 in the case of linear spectroscopy and over 2000 in the case of third-order spectroscopy. A qualitative explanation for the observed effect is given by the extended coupled oscillators model, which takes into account both near-field and radiative interactions between the plasmonic and molecular transitions.
Authors: Andrey Gandman, Robert T Mackin, Bar Cohn, Igor V Rubtsov, Lev Chuntonov

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Surface-Enhanced Dual-Frequency Two-Dimensional Vibrational Spectroscopy of Thin Layers at an Interface

The development of spectroscopic approaches to study molecules at interfaces is important as the molecular properties often differ from those in the bulk. Implementation of surface-enhanced two-dimensional infrared (SE 2DIR) spectroscopy using lithographically fabricated plasmonic nanoarrays is demonstrated for nanometer thick films. The sample, 4-azidobutyrate-N-hydroxysuccinimide ester (azNHS), dispersed in polystyrene was deposited onto the nanoarray. Raw enhancements in the SE 2DIR spectra exceeding 5 × 104 and 1.3 × 103 fold were achieved for the CO and NN peaks, respectively. The field enhancement provided by the nanoarray was sufficient to record cross-peaks in 1 nm thick samples under dilute conditions for azNHS (∼0.1 M). Note that the cross-peaks were recorded for vibrational modes frequency separated by ∼350 cm–1 with the enhancement factor of 4.1 × 104. The effective electric field enhancement factors, measured for NN and CO modes via linear and two nonlinear IR techniques, have similar sample-thickness dependences, which permit using linear spectroscopy for enhancement evaluation. High-quality cross-peak waiting-time dependences were recorded for samples as thin as 1 nm involving several IR reporters demonstrating the applicability of an arsenal of 2DIR approaches, including spectral diffusion, chemical exchange, and relaxation-assisted 2DIR, to interrogate samples in nanometer thick films. The study opens new opportunities in analyzing structures and dynamics of molecules at interfaces.
Authors: Robert T Mackin, Bar Cohn, Andrey Gandman, Joel D Leger, Lev Chuntonov, Igor V Rubtsov

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Communication: Probing the interaction of infrared antenna arrays and molecular films with ultrafast quantum dynamics

Narrowband vibrational molecular transitions interacting with the broadband resonance of infrared plasmonic antennas lead to Fano lineshapes observed in linear (FTIR) and third-order (transient absorption and 2DIR) spectroscopic experiments. Both molecular and plasmonic components are inherently dissipative, and the effects associated with their coupling can be observed, in principle, when measuring the corresponding ultrafast quantum dynamics. We used 2DIR spectroscopy to study the waiting time evolution of quantum coherence excited in the carbonyl stretching modes of rhodium (acetylacetonato) dicarbonyl molecules, which were embedded in an 80 nm-thick polymer film spin-coated on an array of infrared half-wavelength gold antennas. Despite the pronounced Fano lineshapes obtained for the molecular transitions, and up to a four order of magnitude enhancement of the third-order signals, which taken together, indicate the coupling between the plasmonic and molecular transitions, the dynamics of the quantum coherence were identical to that obtained with 3 μm-thick film without the interaction with the plamson mode. This suggests that the coupling rate between the molecular and plasmonic excitations is significantly smaller than the relaxation rates of the molecular excitations monitored in the experiment. Here, the Fano lineshape, observed at the frequency of the molecular transition, can result from the mutual radiation damping of the molecular and plasmon modes.
Authors: Bar Cohn, Amit K Prasad, Lev Chuntonov

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