Broadband Tip-Enhanced Nonlinear Optical Response in a Plasmonic Nanocavity.

We report a significantly broad nonlinear optical response enhanced in a tip-substrate plasmonic nanocavity. Focusing on the near-field second harmonics of the wavelength-tunable femtosecond laser, we demonstrate that the tip-enhancement of nonlinear optical effects efficiently works over the broad wavelength range through the visible to infrared region. We also found that this broadband nonlinear optical property is directly affected not only by the nanometer-scale sharpness of the tip apexes but also by the micrometer-scale surface geometry of the tip shafts. While spatially nonlocal plasmonic modes excited throughout the micrometer-scale tip shafts enhance near-to-mid-infrared incoming light, the radiation of visible-to-near-infrared second harmonics is boosted by localized plasmons at the nanogap. These two plasmonic modes simultaneously affect the excitation and emission processes, realizing the strong and broad enhancement of second harmonic generation. Our results provide a new basis for the physical understanding and fine manipulation of nonlinear optical phenomena enhanced in plasmonic nanocavities.

Before Förster. Initial excitation in photosynthetic light harvesting.

Electronic 2D spectroscopy allows nontrivial quantum effects to be explored in unprecedented detail. Here, we apply recently developed fluorescence detected coherent 2D spectroscopy to study the light harvesting antenna 2 (LH2) of photosynthetic purple bacteria. We report double quantum coherence 2D spectra which show clear cross peaks indicating correlated excitations. Similar results are found for rephasing and nonrephasing signals. Analysis of signal generating quantum pathways leads to the conclusion that, contrary to the currently prevailing physical picture, the two weakly coupled pigment rings of LH2 share the initial electronic excitation leading to quantum mechanical correlation between the two clearly separate absorption bands. These results are general and have consequences for the interpretation of initially created excited states not only in photosynthesis but in all light absorbing systems composed of weakly interacting pigments where the excitation transfer is commonly described by using Förster theory. Being able to spectrally resolve the nonequilibrium dynamics immediately following photoabsorption may provide a glimpse to the systems' transition into the Förster regime.

Molecular ground-state dissociation in the condensed phase employing plasmonic field enhancement of chirped mid-infrared pulses.

Selective bond cleavage via vibrational excitation is the key to active control over molecular reactions. Despite its great potential, the practical implementation in condensed phases have been hampered to date by poor excitation efficiency due to fast vibrational relaxation. Here we demonstrate vibrationally mediated, condensed-phase molecular dissociation by employing intense plasmonic near-fields of temporally-shaped mid-infrared (mid-IR) pulses. Both down-chirping and substantial field enhancement contribute to efficient ladder climbing of the carbonyl stretch vibration of W(CO)6 in n-hexane solution and to the resulting CO dissociation. We observe an absorption band emerging with laser irradiation at the excitation beam area, which indicates that the dissociation is followed by adsorption onto metal surfaces. This successful demonstration proves that the combination of ultrafast optics and nano-plasmonics in the mid-IR range is useful for mode-selective vibrational ladder climbing, paving the way toward controlled ground-state chemistry.

Ultrafast proton/deuteron dynamics in KTaO3 observed with infrared pump-probe spectroscopy: Toward understanding of proton conduction mechanism in solid oxides.

Infrared pump-probe measurement for the OD stretching mode in KTaO3 has been performed. We observed the induced absorption signal corresponding to the 1-2 transition for the first time in oxide crystals in addition to the bleaching signal of the 0-1 transition. Both signals show long decay time of ∼200 ps, and the potential anharmonicity is found to be 3.6%. We also investigated temperature dependence of OH/OD absorption spectra to explore how a proton/deuteron interacts with the surrounding lattice vibrations, and identify the phonon mode which causes the potential fluctuations as a O-Ta-O bending motion. On the basis of the results obtained, we calculate the potential energy surface on which a proton/deuteron moves and discuss the proton conduction mechanism in solid oxides.

Cryogenic Fluorescence Localization Microscopy of Spectrally Selected Individual FRET Pairs in a Water Matrix.

We prepared a pair with a visible-absorbing donor dye and a near-infrared fluorescing acceptor dye. The donor and the acceptor were covalently linked close enough for Förster resonance energy transfer to occur. Under cryogenic conditions at 1.7 K, we observed the fluorescence excitation spectra of the individual pairs in a water matrix. We tested one rhodamine, two Bodipy, and one carbopyronine derivatives as the donor. Among these donors, Bodipy derivatives show the narrowest spectral width of the individuals with respect to the ensemble width. Thus, Bodipy dyes were favorable as the donor for the spectral selection of individual pairs. At 1.7 K, from the several Bodipy-acceptor pairs in the diffraction-limited volume, an individual pair was selected by the fluorescence excitation spectrum of the donor. The spectrally selected pair was localized using the near-infrared fluorescence of the acceptor.

Note: High precision measurements using high frequency gigahertz signals.

Generalized lock-in amplifiers use digital cavities with Q-factors as high as 5 × 10(8) to measure signals with very high precision. In this Note, we show that generalized lock-in amplifiers can be used to analyze microwave (giga-hertz) signals with a precision of few tens of hertz. We propose that the physical changes in the medium of propagation can be measured precisely by the ultra-high precision measurement of the signal. We provide evidence to our proposition by verifying the Newton's law of cooling by measuring the effect of change in temperature on the phase and amplitude of the signals propagating through two calibrated cables. The technique could be used to precisely measure different physical properties of the propagation medium, for example, the change in length, resistance, etc. Real time implementation of the technique can open up new methodologies of in situ virtual metrology in material design.

Generalized lock-in amplifier for precision measurement of high frequency signals.

We herein formulate the concept of a generalized lock-in amplifier for the precision measurement of high frequency signals based on digital cavities. Accurate measurement of signals higher than 200 MHz using the generalized lock-in is demonstrated. The technique is compared with a traditional lock-in and its advantages and limitations are discussed. We also briefly point out how the generalized lock-in can be used for precision measurement of giga-hertz signals by using parallel processing of the digitized signals.

Does ℏ play a role in multidimensional spectroscopy? Reduced hierarchy equations of motion approach to molecular vibrations.

To investigate the role of quantum effects in vibrational spectroscopies, we have carried out numerically exact calculations of linear and nonlinear response functions for an anharmonic potential system nonlinearly coupled to a harmonic oscillator bath. Although one cannot carry out the quantum calculations of the response functions with full molecular dynamics (MD) simulations for a realistic system which consists of many molecules, it is possible to grasp the essence of the quantum effects on the vibrational spectra by employing a model Hamiltonian that describes an intra- or intermolecular vibrational motion in a condensed phase. The present model fully includes vibrational relaxation, while the stochastic model often used to simulate infrared spectra does not. We have employed the reduced quantum hierarchy equations of motion approach in the Wigner space representation to deal with nonperturbative, non-Markovian, and nonsecular system-bath interactions. Taking the classical limit of the hierarchy equations of motion, we have obtained the classical equations of motion that describe the classical dynamics under the same physical conditions as in the quantum case. By comparing the classical and quantum mechanically calculated linear and multidimensional spectra, we found that the profiles of spectra for a fast modulation case were similar, but different for a slow modulation case. In both the classical and quantum cases, we identified the resonant oscillation peak in the spectra, but the quantum peak shifted to the red compared with the classical one if the potential is anharmonic. The prominent quantum effect is the 1-2 transition peak, which appears only in the quantum mechanically calculated spectra as a result of anharmonicity in the potential or nonlinearity of the system-bath coupling. While the contribution of the 1-2 transition is negligible in the fast modulation case, it becomes important in the slow modulation case as long as the amplitude of the frequency fluctuation is small. Thus, we observed a distinct difference between the classical and quantum mechanically calculated multidimensional spectra in the slow modulation case where spectral diffusion plays a role. This fact indicates that one may not reproduce the experimentally obtained multidimensional spectrum for high-frequency vibrational modes based on classical molecular dynamics simulations if the modulation that arises from surrounding molecules is weak and slow. A practical way to overcome the difference between the classical and quantum simulations was discussed.