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Various selective excitation methods for molecular vibrations have been developed based on the characteristics of the applied lasers. In the present work, we coherently and selectively excited molecular vibrations up to 3000 cm−1 by irradiation with a sub-10-fs laser pulse. The spectral shaping of this laser pulse enabled us to selectively excite only the target vibrational frequency range (of the model compounds acetonitrile and benzene). Furthermore, the coherent molecular vibrational dynamics were compared between selective and nonselective excitation. The coherence of the molecular vibration persisted until 2–3 ps after photoexcitation, with the lifetime of this coherence being independent of whether the coherent molecular vibration was selective or nonselective excitation.

When an electric field is applied between two electrodes facing each other immersed in a liquid, the interfacial Pockels effect, a refractive index change proportional to the electric field, occurs in the electric double layer at the liquid–electrode interface. Here, we report that the Pockels effect of interfacial water can be observed even when an electric field is applied parallel to the surface of a “single” electrode in an electrolyte solution. This is a non-trivial result since the electric field parallel to the interface should not cause a broken spatial inversion symmetry, which is required for the Pockels effect. The Pockels signal was detected as a change in the transmitted light intensity due to the field-induced spectral shift of the interference fringes of the transparent conductive oxide electrode layer on a glass substrate. The magnitude of the signal increased as it approached the ends of the electrode, and the sign reversed across the center of the electrode. The electric field distribution calculated from the interfacial potential difference due to the in-plane parallel current showed that an electric field perpendicular to the interface was induced, whose distribution was consistent with the position dependence of the Pockels signal. A similar phenomenon was also observed for a single copper electrode, confirming that this is a universal effect.

The journal Applied Sciences was established in 2011, covering five broad subjects and thirty-two narrow sections [...]

The Pockels coefficient of interfacial water between bulk water and a Ti electrode was estimated from the electroreflectance spectra (ΔR/R) to be r13≈−150 pm/V as the maximum value of magnitude, which is comparable in magnitude to the largest coefficient for electrode interfacial water, i.e., 200 pm/V for interfacial water on a transparent oxide electrode. This Pockels signal increased by a factor of about ±3 by applying a DC bias voltage of ±1 V. The reflectance (R) of the Ti electrode had a dip structure in the UV region (3.5–4.5 eV) due to the interference of a 14 nm thick surface oxide film, and the ΔR/R spectra in aqueous electrolyte solution showed a large reflectance change in the UV region with a dispersive shape due to the contribution of the TiO2 film. The reproducibility of the electroreflectance experiment was high, suggesting that the surface oxide film contributes to the large Pockels effect of interfacial water and the robustness of the electrode.

A simple scheme for single-channel coherent perfect absorption (CPA) of transparent materials is proposed and experimentally realized using total internal reflection by grazing incidence, with a single dielectric layer sandwiched by semi-infinite dielectric layers. In a 1.48-µm thick polyvinylpyrrolidone (PVP) film, dip-coated on a MgF2 substrate both transparent in the visible, reflectance dips due to nearly 90% absorption by single-channel CPA were observed in the wavelength range of 370–800 nm, with white light from a Xe lamp incident on the side face of the substrate and extracted from the other side through multiple reflections in the PVP layer. This is a simple and inexpensive CPA scheme, and it is expected to have various applications by changing the substrate/polymer material or dispersing molecules in the polymer film. This paper also provides a design guideline for grazing-incidence waveguide-mode sensors using transparent dielectric materials.

The optical Pockels effect is a change in the refractive index proportional to an applied electric field. As a typical example of the interfacial Pockels effect occurring at interfaces where the spatial inversion symmetry is broken, it is known that water in the electric double layer (EDL) on the transparent oxide electrode surface has a large Pockels coefficient, but the physical factors that determine its size are not clear. Therefore, we experimentally studied the Pockels effect of water and other characteristic liquids—formamide (FA), methylformamide (NMF) (these two have larger static dielectric constants than water), dimethylformamide (DMF), and an ionic liquid that is itself salts (IL, [BMIM] [BF4])—and evaluated their Pockels coefficients in the EDL on the transparent electrode surface. The magnitude of the Pockels coefficient was found to be in the order of water, DMF, FA, NMF, and IL, with the magnitude of the static dielectric constant not being an important factor.

We studied spectra of the amplified signal from a noncollinear optical parametric amplifier (NOPA) based on a Ti:sapphire laser and BBO crystal gain medium. The signal shows characteristic structures with periodic intensity variations in the signal during the parametric amplification processes in a BBO crystal. This phenomenon is attributed to the stimulated Raman process excited by the pump pulse affected by the phase-matching condition of four-wave mixing. The effect of this stimulated Raman process on optical parametric amplification and on final pulse compression of the signal was analyzed. The results demonstrate that caution must be taken when constructing a NOPA. Specifically, great care must be taken not to use mirrors with non-uniform spectral reflectivity for obtaining a stable pulse in terms of both temporal and spectral shapes.

The difference absorption spectrum (DAS) of porphyrin molecules (tetraphenyl-porphyhrin sulfonic acid, TPPS) in aqueous solution induced by continuous wave laser irradiation has been reported previously. It was interpreted that the DAS was caused by the formation of TPPS aggregates induced by laser irradiation. However, transient spectra similar in their shape have already been reported and are attributed to the excited-state absorption and saturable absorption (SA) effects due to the triplet state formation in TPPS. In the present study, we investigated the triplet quenching effect by O2 on the DAS of TPPS aqueous solution and revealed that it originated from the triplet state formation. We also found that mixing the appropriate amount of MeOH and NaOH in TPPS aqueous solution increased its absorbance change by more than 50 times. This may be due to the decrease in dissolved oxygen concentration by mixing them. This result suggests the possibility of controlling the performance of NLO materials by adjusting the solvent mixture ratio and base/acid concentration.

In the research on application of an optical modulator used for information communication, materials having a large Pockels effect, a refractive index change proportional to the electric-field, are required. It is known that the interfacial water on the surface of transparent oxide electrodes has a giant Pockels coefficient, which is an order of magnitude larger than the solid Pockels crystals practically used. It is important to know the Pockels coefficient of water on not only an oxide surface, but also a metal surface to understand the mechanism of the interfacial Pockels effect of water. However, a method has not yet been established for evaluating the coefficient of water–metal interface. Here we present an evaluation method of the Pockels coefficient of interfacial water on a metal (silver) surface from the spectral shift of the surface plasmon polariton resonance due to electric-field induced refractive index change of the interfacial water. The Pockels coefficient of interfacial water on Ag was evaluated as |r33|=5±1 pm/V, without need for exact knowledge of the thickness of the interfacial layer (electric double layer of water) as long as the penetration depth of the plasmon is larger than the thickness.

A highly efficient light-induced aggregation of porphyrin molecules in solution was recently reported for 4-[10,15,20-tris(4-sulfophenyl)-21,24-dihydroporphyrin-5-yl]benzenesulfonic acid (TPPS). Here, we demonstrate that rhodamine 6G (R6G) and pseudoisocyanine (PIC) also show efficient light-induced aggregation in unsaturated aqueous solution, being detected with a multichannel lock-in amplifier as the absorbance decrease/increase in the monomers/aggregates, induced by a laser at 633 nm, which is non-resonant off their main monomer absorption wavelengths. The light-induced aggregation states are H-aggregates that are hardly formed in the thermal equilibrium. The similar absorbance changes are absent in the monomer molecules fixed in polyvinyl alcohol (PVA) films. The aggregation efficiency defined as ( Δ A / A ) / ( U t r a p / k B T ) , where A is the absorbance of the monomers, Δ A is the absorbance increase in the aggregates, U t r a p is the optical gradient force potential, and k B T is the thermal energy at room temperature, is approximately 100 for R6G and 500 for PIC, which are much smaller than that of TPPS.

Two decades have passed since the first year of the 21st century [...]

Highly sensitive broadband photothermal spectroscopy with a white-light lamp as the excitation source was developed by combining a Sagnac interferometer and balanced detection with a photothermal deflection method. A probe beam was split by a birefringent crystal CaCO3 into signal and reference beams with a balanced intensity. This balanced detection enabled the measurement of photoexcited thermal relaxation spectra of materials in the air over the whole visible range in the weak excitation limit 50 µW/cm2. The photothermal excitation spectrum of Eu2+-doped CaAlSiN3 phosphors (CASN:Eu2+) with a high luminescent quantum efficiency was measured to be distinctly different from the photoluminescence excitation spectrum which reflects the absorption spectrum, revealing the thermal relaxation mechanism of the phosphor. Assuming a typical non-radiative relaxation from the higher excited states to the lowest excited state and successively to the ground state, it is demonstrated that the photoluminescence efficiency of the phosphors is readily evaluated simply by comparing the photothermal and photoluminescence excitation spectra.

This paper introduces and discusses the main aspects of multicolored femtosecond pulse generation using cascaded four-wave mixing (CFWM) in transparent bulk materials. Theoretical analysis and semi-quantitative calculations, based on the phase-matching condition of the four-wave mixing process, explain the phenomena well. Experimental studies, based on our experiments, have shown the main characteristics of the multicolored pulses, namely, broadband spectra with wide tunability, high stability, short pulse duration and relatively high pulse energy. Two-dimensional multicolored array generation in various materials are also introduced and discussed.

Chemical bond breaking and formation during chemical reactions can be observed using “transition state spectroscopy”. Comparing the measurement result of the transition state spectroscopy with the simulation result of single direct-dynamics trajectory, we have elucidated the reaction dynamics of Claisen rearrangement of allyl vinyl ether. Observed the reaction of the neat sample liquid, we have estimated the time constants of transformation from straight-chain structure to aromatic-like six-membered ring structure forming the C1-C6 bond. The result clarifies that the reaction proceeds via three steps taking longer time than expected from the gas phase calculation. This finding provides new hypothesis and discussions, helping the development of the field of reaction mechanism analysis.

Label-free confocal photothermal (CPT) microscopy was utilized for the first time to investigate malignancy in mouse skin cells. Laser diodes (LDs) with 405 nm or 488 nm wavelengths were used as pumps, and a 638 nm LD was used as a probe for the CPT microscope. A Grey Level Cooccurrence Matrix (GLCM) for texture analysis was applied to the CPT images. Nine GLCM parameters were calculated with definite definitions for the intracellular super-resolved CPT images, and the parameters Entropy, Contrast, and Variance were found to be most suited among the nine parameters to discriminate clearly between healthy cells and malignant cells when a 405 nm pump was used. Prominence, Variance, and Shade were most suited when a pump wavelength of 488 nm was used.

Principles and information obtained by ultrafast spectroscopy and scheme of optical parametric amplifier are discussed. Realization of ultrashort visible and ultraviolet lasers based on the parametric processes are discussed.

We have reviewed the generation and amplification of wavelength-tunable multicolored femtosecond laser pulses using cascaded four-wave mixing (CFWM) in transparent bulk media, mainly concentrating on our recent work. Theoretical analysis and calculations based on the phase-matching condition could explain well the process semi-quantitatively. The experimental studies showed: (1) as many as fifteen spectral up-shifted and two spectral down-shifted sidebands were obtained simultaneously with spectral bandwidth broader than 1.8 octaves from near ultraviolet (360 nm) to near infrared (1.2 μm); (2) the obtained sidebands were spatially separated well and had extremely high beam quality with M2 factor better than 1.1; (3) the wavelengths of the generated multicolor sidebands could be conveniently tuned by changing the crossing angle or simply replacing with different media; (4) as short as 15-fs negatively chirped or nearly transform limited 20-fs multicolored femtosecond pulses were obtained when one of the two input beams was negatively chirped and the other was positively chirped; (5) the pulse energy of the sideband can reach a μJ level with power stability better than 1% RMS; (6) broadband two-dimensional (2-D) multicolored arrays with more than ten periodic columns and more than ten rows were generated in a sapphire plate; (7) the obtained sidebands could be simultaneously spectra broadened and power amplified in another bulk medium by using cross-phase modulation (XPM) in conjunction with four-wave optical parametric amplification (FOPA). The characterization showed that this is interesting and the CFWM sidebands generated by this novel method have good enough qualities in terms of power stability, beam quality, and temporal features suited to various experiments such as ultrafast multicolor time-resolved spectroscopy and multicolor-excitation nonlinear microscopy.

To directly access the dynamics of electron distribution near the Fermi-surface after plasmon excitation, pump-probe spectroscopy was performed by pumping plasmons on noble-metal films and probing the interband transition. Spectral change in the interband transitions is sensitive to the electron distribution near the Fermi-surface, because it involves the d valence-band to the conduction band transitions and should reflect the k-space distribution dynamics of electrons. For the continuous-wave pump and probe experiment, the plasmon modulation spectra are found to differ from both the current modulation and temperature difference spectra, possibly reflecting signatures of the plasmon wave function. For the femtosecond-pulse pump and probe experiment, the transient spectra agree well with the known spectra upon the excitation of the respective electrons resulting from plasmon relaxation, probably because the lifetime of plasmons is shorter than the pulse duration.

Since its introduction in 2010, self-referenced spectral interferometry (SRSI) has turned out to be an analytical, sensitive, accurate, and fast method for characterizing the temporal profile of femtosecond pulses. We review the underlying principle and the recent progress in the field of SRSI. We present our experimental work on this method, including the development of self-diffraction (SD) effect-based SRSI (SD-SRSI) and transient-grating (TG) effect-based SRSI (TG-SRSI). Three experiments based on TG-SRSI were performed: (1) We built a simple TG-SRSI device and used it to characterize a sub-10 fs pulse with a center wavelength of 1.8 μm. (2) On the basis of the TG effect, we successfully combined SRSI and frequency-resolved optical gating (FROG) into a single device. The device has a broad range of application, because it has the advantages of both SRSI and FROG methods. (3) Weak sub-nanojoule pulses from an oscillator were successfully characterized using the TG-SRSI device, the optical setup of which is smaller than the palm of a hand, making it convenient for use in many applications, including sensor monitoring the pulse profile of laser systems. In addition, the SRSI method was extended for single-shot characterization of the temporal contrast of ultraintense and ultrashort laser pulses.

We previously reported that multiply-primed rolling circle amplification (MRPCA) using modified random RNA primers can amplify tiny amounts of circular DNA without producing any byproducts. However, contaminating DNA in recombinant Phi29 DNA polymerase adversely affects the outcome of MPRCA, especially for negative controls such as non-template controls. The amplified DNA in negative control casts doubt on the result of DNA amplification. Since Phi29 DNA polymerase has high affinity for both single-strand and double-stranded DNA, some amount of host DNA will always remain in the recombinant polymerase. Here we describe a procedure for preparing Phi29 DNA polymerase which is essentially free of amplifiable DNA. This procedure is realized by a combination of host DNA removal using appropriate salt concentrations, inactivation of amplifiable DNA using ethidium monoazide, and irradiation with visible light from a light-emitting diode lamp. Any remaining DNA, which likely exists as oligonucleotides captured by the Phi29 DNA polymerase, is degraded by the 3'-5' exonuclease activity of the polymerase itself in the presence of trehalose, used as an anti-aggregation reagent. Phi29 DNA polymerase purified by this procedure has little amplifiable DNA, resulting in reproducible amplification of at least ten copies of plasmid DNA without any byproducts and reducing reaction volume. This procedure could aid the amplification of tiny amounts DNA, thereby providing clear evidence of contamination from laboratory environments, tools and reagents.

Multiferroic hexagonal manganites ReMnO3 studied by optics are reviewed. Their electronic structures were revealed by static linear and nonlinear spectra. Two transitions located at ~1.7 eV and ~2.3 eV have been observed and attributed to the interband transitions from the lower-lying Mn3+dxy/dx2-y2 and dxz/dyz states to the Mn3+d3z2-r2 state, respectively. These so-called d-d transitions exhibit a blueshift as decreasing temperatures and an extra blueshift near TN. This dramatic change indicates that the magnetic ordering seriously influences the electronic structure. On the other hand, the ultrafast optical pump-probe spectroscopy has provided the important information on spin-charge coupling and spin-lattice coupling. Because of the strongly correlation between electronic structure and magnetic ordering, the amplitude of the initial rising component in ΔR/R shows striking changes at the vicinity of TN. Moreover, the coherent optical and acoustic phonons were observed on optical pump-probe spectroscopy. Both the amplitude and dephasing time of coherent phonons also exhibit significant changes at TN, which provide the evidence for spin-lattice interaction in these intriguing materials.

In the first section of this Chapter, the basics of nonlinear optical (NLO) processes are systematically described. Then the generation of the visible pulse utilizing the NLO processes is described and ultrafast spectroscopy using the visible pulse is discussed. By using such short pulse, fast chemical reactions, which cannot be identified by utilizing strobe light or flash lamp, can be studied. After the development of femtosecond lasers, they have been widely applied to observe the transition state of various chemical reactions. In the near infrared (NIR) region, a commercial light source of Ti:sapphire laser is available as a femtosecond light source, but not available in the visible and ultraviolet (UV) regions. In this article, we report our development of sub 10 fs visible-NIR, UV, and deep-ultraviolet (DUV) pulses and their applications to ultrafast spectroscopy.

Applied sciences cover many interdisciplinary fields that put basic sciences to application and make big changes by taking the one not-so-small step from “knowing how” to “knowing how-to”, the serendipity of which is often intriguing. Applied sciences are so deeply entrenched in almost all aspects of our daily lives. To provide an advanced forum for scholars all over the world to discuss and communicate the cutting-edge development in this field, on behalf of the Editorial Board members, I am honored to introduce Applied Sciences, a scholarly, peer-reviewed open access journal. [...]