Excitonic effects in two-dimensional vibrational spectra of liquid formamide

The linear and two-dimensional infrared (2DIR) responses of the amide I vibrational mode in liquid formamide are investigated experimentally and theoretically using molecular dynamics simulations. The recent method based on the numerical integration of the Schrödinger equation is employed to calculate the 2DIR spectra. Special attention is devoted to the interplay of the structural dynamics and the excitonic nature of the amide I modes in determining the optical response of the studied system. In particular, combining experimental data, simulated spectra and analysis of the simulated atomic trajectory in terms of a transition dipole coupling model, we provide a convincing explanation of the peculiar features of the 2DIR spectra, which show a substantial increase of the antidiagonal bandwidth with increasing frequency. We point out that, at variance with liquid water, the 2DIR spectral profile of formamide is determined more by the excitonic nature of the vibrational states than by the fast structural dynamics responsible for the frequency fluctuations

Resonant enhancement of second harmonic generation in the mid-infrared using localized surface phonon polaritons in sub-diffractional nanostructures

We report on strong enhancement of mid-infrared second harmonic generation (SHG) from SiC nanopillars due to the resonant excitation of localized surface phonon-polaritons within the Reststrahlen band. The magnitude of the SHG peak at the monopole mode experiences a strong dependence on the resonant frequency beyond that described by the field localization degree and the dispersion of linear and nonlinear-optical SiC properties. Comparing the results for the identical nanostructures made of 4H and 6H SiC polytypes, we demonstrate the interplay of localized surface phonon polaritons with zone-folded weak phonon modes of the anisotropic crystal. Tuning the monopole mode in and out of the region where the zone-folded phonon is excited in 6H-SiC, we observe a prominent increase of the already monopole-enhanced SHG output when the two modes are coupled. Envisioning this interplay as one of the showcase features of mid-infrared nonlinear nanophononics, we discuss its prospects for the effective engineering of nonlinear-optical materials with desired properties in the infrared spectral range.Comment: 16 pages, 3 figure

Second harmonic generation from strongly coupled localized and propagating phonon-polariton modes

We experimentally investigate second harmonic generation from strongly coupled localized and propagative phonon polariton modes in arrays of silicon carbide nanopillars. Our results clearly demonstrate the hybrid nature of the system's eigenmodes and distinct manifestation of strong coupling in the linear and nonlinear response. While in linear reflectivity the intensity of the two strongly-coupled branches is essentially symmetric and well explained by their respective localized or propagative components, the second harmonic signal presents a strong asymmetry. Analyzing it in detail, we reveal the importance of interference effects between the nonlinear polarization terms originating in the bulk and in the phonon polariton modes, respectively.Comment: 7 pages, 4 figure

Structure and Reactivity of α-Al₂O₃(0001) Surfaces: How Do Al-I and Gibbsite-like Terminations Interconvert?

The α-Al2O3(0001) surface has been extensively studied because of its significance in both fundamental research and application. Prior work suggests that in ultra-high-vacuum (UHV), in the absence of water, the so-called Al–I termination is thermodynamically favored, while in ambient, in contact with liquid water, a Gibbsite-like layer is created. While the view of the α-Al2O3(0001)/H2O(l) interface appears relatively clear in theory, experimental characterization of this system has resulted in estimates of surface acidity, i.e., isoelectric points, that differ by 4 pH units and surface structure that in some reports has non-hydrogen-bonded surface aluminol (Al–OH) groups and in others does not. In this study, we employed vibrational sum frequency spectroscopy (VSFS) and density functional theory (DFT) simulation to study the surface phonon modes of the differently terminated α-Al2O3(0001) surfaces in both UHV and ambient. We find that, on either water dosing of the Al–I in UHV or heat-induced dehydroxylation of the Gibbsite-like in ambient, the surfaces do not interconvert. This observation offers a new explanation for disagreements in prior work on the α-Al2O3(0001)/liquid water interface─different preparation methods may create surfaces that do not interconvert─and shows that the surface phonon spectral response offers a novel probe of interfacial hydrogen bonding structure

Second Harmonic Generation from Grating-Coupled Hybrid Plasmon-Phonon Polaritons

Polaritons can provide strong optical field enhancement allowing to boost light-matter interaction. Here, we experimentally observe enhancement of mid-infrared second-harmonic generation (SHG) using grating-coupled surface phonon polaritons of the 6H-SiC surface. In our experiment, we measure the SHG along the polariton dispersion by changing the incidence angle of the excitation beam. We observe hybridization between the propagating surface phonon polaritons and localized plasmon resonances in the gold grating, evidenced by the modification of the polariton dispersion as we change the area ratio of grating and substrate. Design options for engineering the plasmon-phonon polariton hybridization are discussed. Overall, we find a rather low yield of polariton-enhanced SHG in this geometry compared to prism-coupling and nanostructures, and discuss possible origins

Hyperbolic shear polaritons in low-symmetry crystals

The lattice symmetry of a crystal is one of the most important factors in determining its physical properties. Particularly, low-symmetry crystals offer powerful opportunities to control light propagation, polarization and phase. Materials featuring extreme optical anisotropy can support a hyperbolic response, enabling coupled light–matter interactions, also known as polaritons, with highly directional propagation and compression of light to deeply sub-wavelength scales. Here we show that monoclinic crystals can support hyperbolic shear polaritons, a new polariton class arising in the mid-infrared to far-infrared due to shear phenomena in the dielectric response. This feature emerges in materials in which the dielectric tensor cannot be diagonalized, that is, in low-symmetry monoclinic and triclinic crystals in which several oscillators with non-orthogonal relative orientations contribute to the optical response. Hyperbolic shear polaritons complement previous observations of hyperbolic phonon polaritons in orthorhombic and hexagonal crystal systems, unveiling new features, such as the continuous evolution of their propagation direction with frequency, tilted wavefronts and asymmetric responses. The interplay between diagonal loss and off-diagonal shear phenomena in the dielectric response of these materials has implications for new forms of non-Hermitian and topological photonic states. We anticipate that our results will motivate new directions for polariton physics in low-symmetry materials, which include geological minerals, many common oxides and organic crystals, greatly expanding the material base and extending design opportunities for compact photonic devices

Long-wave infrared super-resolution wide-field microscopy using sum-frequency generation

Super-resolution microscopy in the visible is an established powerful tool in various disciplines. In the long-wave infrared (LWIR) spectral range, however, no comparable schemes have been demonstrated to date. In this work, we experimentally demonstrate super-resolution microscopy in the LWIR range (λIR ≈ 10–12 μm) using IR-visible sum-frequency generation. We operate our microscope in a wide-field scheme and image localized surface phonon polaritons in 4H-SiC nanostructures as a proof-of-concept. With this technique, we demonstrate an enhanced spatial resolution of ~λIR/9, enabling to resolve the polariton resonances in individual sub-diffractional nanostructures with sub-wavelength spacing. Furthermore, we show that this resolution allows us to differentiate between spatial patterns associated with different polariton modes within individual nanostructures

Ultrafast relaxation dynamics of the antiferrodistortive phase in Ca doped SrTiO3

The ultrafast dynamics of the octahedral rotation in Ca:SrTiO3 is studied by time resolved x-ray diffraction after photo excitation over the band gap. By monitoring the diffraction intensity of a superlattice reflection that is directly related to the structural order parameter of the soft-mode driven antiferrodistortive phase in Ca:SrTiO3, we observe a ultrafast relaxation on a 0.2 ps timescale of the rotation of the oxygen octahedron, which is found to be independent of the initial temperaure despite large changes in the corresponding soft-mode frequency. A further, much smaller reduction on a slower picosecond timescale is attributed to thermal effects. Time-dependent density-functional-theory calculations show that the fast response can be ascribed to an ultrafast displacive modification of the soft-mode potential towards the normal state, induced by holes created in the oxygen 2p states

Two-Dimensional Spectroscopy of Extended Molecular Systems: Applications to Energy Transport and Relaxation in an α-Helix

A simulation study of the coupled dynamics of amide I and amide II vibrations in an α-helix dissolved in water shows that two-dimensional (2D) infrared spectroscopy may be used to disentangle the energy transport along the helix through each of these modes from the energy relaxation between them. Time scales for both types of processes are obtained. Using polarization-dependent 2D spectroscopy is an important ingredient in the method we propose. The method may also be applied to other two-band systems, both in the infrared (collective vibrations) and the visible (excitons) parts of the spectrum.