Laser Excitation Technique Research Articles

Columnar excitation fluorescence microscope for accurate evaluation of quantum properties of color centers in bulk materials

Color centers in wide band-gap semiconductors, which have superior quantum properties even at room temperature and atmospheric pressure, have been actively applied to quantum sensing devices. Characterizing the quantum properties of the color centers in the semiconductor materials and ensuring that these properties are uniform over a wide area are key issues for developing quantum sensing devices based on color centers. In this article, we have developed an optics design protocol optimized for evaluating the quantum properties of color centers and have used this design approach to develop a new microscopy system called columnar excitation fluorescence microscope (CEFM). The essence of this system is to maximize the amount of fluorescence detection of polarized color centers, which is achieved by large-volume and uniform laser excitation along the sample thickness with sufficient laser power density. This laser excitation technique prevents undesirable transitions to undesirable charge states and undesirable light, such as unpolarized color center fluorescence, while significantly increasing the color center fluorescence. This feature enables fast measurements with a high signal-to-noise ratio, making it possible to evaluate the spatial distribution of quantum properties across an entire mm-size sample without using a darkroom, which is difficult with typical confocal microscope systems.

High resolution electronic spectroscopy of uranium mononitride, UN.

The isoelectronic molecules UN and UO+ are known to have Ω = 3.5 and Ω = 4.5 ground states, respectively (where Ω is the unsigned projection of the electronic angular momentum along the internuclear axis). A ligand field theory model has been proposed to account for the difference [Matthew and Morse, J. Chem. Phys. 138, 184303 (2013)]. The ground state of UO+ arises from the U3+(5f3(4I4.5))O2- configuration. Owing to the higher nominal charge of the N3- ligand, the U3+ ion in UN is stabilized by promoting one of the 5f electrons to the more polarizable 7s orbital, reducing the repulsive interaction with the ligand and rendering U3+(5f27s(4H3.5))N3- the lowest energy configuration. In the present work, we have advanced the characterization of the UN ground state through studies of two electronic transitions, [18.35]4.5-X(1)3.5 and [18.63]4.5-X(1)3.5, using sub-Doppler laser excitation techniques with fluorescence detection. Spectra were recorded under field-free conditions and in the presence of static electric or magnetic fields. The ground state electric dipole moment [μ = 4.30(2) D] and magnetic ge-factor [2.160(9)] were determined from these data. These values were both consistent with the 5f27s configurational assignment. Dispersed fluorescence measurements were used to determine vibrational constants for the ground and first electronically excited states. Electric dipole moments and magnetic ge-factors are also reported for the higher-energy electronically excited states.

Electronic Spectroscopy and Photoionization of LiMg.

Dimers consisting of an alkali metal bound to an alkaline earth metal are of interest from the perspectives of their bonding characteristics and their potential for being laser cooled to ultracold temperatures. There have been experimental and theoretical studies of many of these species, but spectroscopic data for LiMg and the LiMg+ cation are sparse. In this study, rotationally resolved electronic spectra for LiMg are presented. The ground state is confirmed to be X12Σ+ and observations of low-lying electronically excited states are reported for the first time. Reexamination of transitions in the near-UV spectral range indicates that previous band assignments should be revised. Two-color laser excitation techniques were used to determine an ionization energy of 4.7695(4) eV. This value is 1.2 eV below the previously reported experimental estimate. Vibrationally resolved spectra were obtained for LiMg+, yielding molecular constants that were consistent with a substantial strengthening of the bond on ionization.

Mid-Infrared Amplified Spontaneous Emission from the f′ 0g+ (1D2) Ion-Pair State and Spectroscopic Characterization of the Shallow 0g+ (ab) Valence State of I2

In this paper, we describe amplified spontaneous emission (ASE) from the f' 0g+ (1D2) ion-pair state of I2 populated through a two-step laser excitation technique via the B 3Π(0u+) valence state. The intense infrared emission propagating in the direction of the incident laser beam is assigned to the ASE transition from the f' 0g+ (1D2) state to the F' 0u+ (1D2) ion-pair state. The subsequent ultraviolet fluorescence transition from the F' 0u+ (1D2) state to the 0g+ (bb) state as well as the 0g+ (ab) state is also reported. By Franck-Condon simulation of the cascading F' 0u+ (1D2) → 0g+ (bb) band, we determine the population distributions in the F' 0u+ (1D2) state generated by ASE, which are consistent with the intensity profile of the mid-infrared ASE spectrum. Finally, employing these vibrational distributions for the F' 0u+ (1D2) state, spectral parameters for the shallow 0g+ (ab) state are derived.

In-cell single-molecule FRET measurements reveal three conformational state changes in RAF protein

BackgroundThe structures of proteins are intimately related to their functions. Significant efforts have been dedicated to the structural investigation of proteins, mainly those of purified proteins in in vitro environments. Proteins function in living cells and thus protein structures must be regulated by interactions with various molecules, some of which participate in reaction networks, depending on the states, conditions, or actions of the cell. Therefore, it is very important to understand the structural behavior of proteins in living cells. MethodsSingle-molecule Förster resonance energy transfer (smFRET) measurements were conducted using the alternative laser excitation (ALEX) technique. smFRET distributions of cytosolic Rapidly Accelerated Fibrosarcoma (RAF) proteins in living HeLa cells were obtained with exclusion of the negative effects of photobleached fluorophores and incompletely labeled proteins on smFRET. ResultssmFRET histograms of wildtype (wt) RAF in live cells exhibited two major peaks, whereas that of the S621A mutant, which has been thought to have an expanded structure, was almost single-peaked. A population shift involving the peaks for wt RAF was detected upon epidermal growth factor stimulation. Spontaneous transitions between the conformational states corresponding to the two peaks were also detected using the FRET-two-channel kernel-based density distribution estimator method in comparison to static double-stranded DNA samples. ConclusionsCytosolic CRAF has at least three conformational states; in addition to the closed and open forms, the fully-open form was distinctly specified. Based on the results, we propose a speculative structural model for CRAF. General significanceStructural distribution and changes to proteins in live cells as a result of intracellular interactions were successfully identified. smFRET using ALEX is applicable to any other cytosolic proteins.

Formation of Tm-Y centers in CaF2-YF3:Tm3+ solid-solution crystals

The spectroscopic properties of Tm3+ optical centers at the 3F4-3H6 two-micron transition in CaF2-YF3:Tm3+ solid-solution crystals are studied by the selective laser excitation technique. The low-temperature (14 K, 77 K) time-resolved fluorescence spectra and lifetimes of several observed optical centers of thulium ions are measured under selective excitation at the 3H6-3H5 transition. Four optical centers in the CaF2-YF3:Tm3+ crystal are identified, namely, a new long-lifetime (3F4 level lifetime longer than 100 ms) optical center similar to a center observed in CaF2:Tm3+ crystals and three spectrally different clustered centers, one of which has an analogue in the CaF2:Tm3+ crystal and two others are new complex Tm-Y clusters.

Investigations on flexural wave propagation and attenuation in a modified one-dimensional acoustic black hole using a laser excitation technique

Abstract Acoustic Black Holes (ABHs), as a new type of passive structure for vibration damping enhancement and noise attenuation, have been drawing increasing attentions of many researchers. Due to the difficulty in manufacturing the sharp edges required by the ABH structures, it is important to understand the wave propagation and attenuation process in the presence of damping layers in non-ideal ABHs with a truncated edge. In this paper, an analytical expression of the wave reflection coefficient in a modified one-dimensional ABH is derived and a time-domain experimental method based on a laser excitation technique is used to visualize the wave propagation. In the experimental studies, the flexural waves in the ABH were excited by a scanning pulse laser and measured by a Laser Doppler Vibrometer (LDV). The incident wave and reflected wave were separated from the measured original wave field and the decrease of the wave velocity in the ABH was exhibited. The reflection coefficient was calculated from the ratio of the amplitude of the reflected wave to that of the incident wave for different ABH parameters and different thicknesses of the damping layer. The measured reflection coefficients were used to identify the unknown coefficients in the theoretical formula. The results confirm that there exists an optimal thickness for the damping layer, which leads to the minimum wave reflection. Based on the laser-induced visualization technique and various signal processing and feature extraction methods, the entire process of the wave propagation in a non-ideal one-dimensional ABH structure can be visualized and scrutinized.

Lifetime measurements using two-step laser excitation for high-lying even-parity levels and improved theoretical oscillator strengths in Y ii

We report new time-resolved laser-induced fluorescence lifetime measurements for 22 highly excited even-parity levels in singly ionized yttrium (Y II). To populate these levels belonging to the configurations 4d6s, 5s6s 4d5d, 5p2, 4d7s and 4d6d, a two-step laser excitation technique was used. Our previous pseudo-relativistic Hartree-Fock model (Biemont et al. 2011) was improved by extending the configuration interaction up to n = 10 to reproduce the new experimental lifetimes. A set of semi-empirical oscillator strengths extended to transitions falling in the spectral range λλ194-3995 nm, depopulating these 22 even-parity levels in Y II, is presented and compared to the values found in the Kurucz's data base (Kurucz 2011). (Less)

Au-S Bonding Revealed from the Characterization of Diatomic Gold Sulfide, AuS.

Gold monosulfide, AuS, has been detected and characterized in the gas phase using optical spectroscopy. The symmetries of the ground and low-lying electronic excited states have been determined by application of a synergy of hot and cold laser excitation techniques. The electronic spectra are assigned to progressions in four band systems associated with excitations from the X(2)Πi ((2σ)(2)(2π)(3)) ground state to the A(2)Σ(+) state arising from the (2σ)(1)(2π)(4) configuration and to the a(4)Σ(-), B(2)Σ(-), and C(2)Δi states arising from the (2σ)(2)(2π)(2)(3σ*)(1) configuration. The bond length and dissociation energy of the ground X(2)Πi state are determined to be 2.156(2) Å and 298 ± 2 kJ/mol, respectively. A molecular orbital correlation diagram is used to rationalize the energy ordering of the excited states and the associated harmonic frequencies.

Nucleosome Core Particle Disassembly and Assembly Kinetics Studied Using Single-Molecule Fluorescence

The stability of the nucleosome core particle (NCP) is believed to play a major role in regulation of gene expression. To understand the mechanisms that influence NCP stability, we studied stability and dissociation and association kinetics under different histone protein (NCP) and NaCl concentrations using single-pair Förster resonance energy transfer and alternating laser excitation techniques. The method enables distinction between folded, unfolded, and intermediate NCP states and enables measurements at picomolar to nanomolar NCP concentrations where dissociation and association reactions can be directly observed. We reproduced the previously observed nonmonotonic dependence of NCP stability on NaCl concentration, and we suggest that this rather unexpected behavior is a result of interplay between repulsive and attractive forces within positively charged histones and between the histones and the negatively charged DNA. Higher NaCl concentrations decrease the attractive force between the histone proteins and the DNA but also stabilize H2A/H2B histone dimers, and possibly (H3/H4)2 tetramers. An intermediate state in which one DNA arm is unwrapped, previously observed at high NaCl concentrations, is also explained by this salt-induced stabilization. The strong dependence of NCP stability on ion and histone concentrations, and possibly on other charged macromolecules, may play a role in chromosomal morphology.

Target dependent femtosecond laser plasma implantation dynamics in enabling silica for high density erbium doping.

Chemical dissimilarity of tellurium oxide with silica glass increases phase separation and crystallization tendency when mixed and melted for making a glass. We report a novel technique for incorporating an Er3+-doped tellurite glass composition into silica substrates through a femtosecond (fs) laser generated plasma assisted process. The engineered material consequently exhibits the spectroscopic properties of Er3+-ions, which are unachievable in pure silica and implies this as an ideal material for integrated photonics platforms. Formation of a well-defined metastable and homogeneous glass structure with Er3+-ions in a silica network, modified with tellurite has been characterized using high-resolution cross-sectional transmission electron microscopy (HRTEM). The chemical and structural analyses using HRTEM, Rutherford backscattering spectrometry (RBS) and laser excitation techniques, confirm that such fs-laser plasma implanted glasses may be engineered for significantly higher concentration of Er3+-ions without clustering, validated by the record high lifetime-density product 0.96 × 1019 s.cm−3. Characterization of planar optical layers and photoluminescence emission spectra were undertaken to determine their thickness, refractive indices and photoluminescence properties, as a function of Er3+ concentration via different target glasses. The increased Er3+ content in the target glass enhance the refractive index and photoluminescence intensity of the modified silica layer whilst the lifetime and thickness decrease.

Kinetics of optically pumped Ar metastables.

Optically pumped lasers that use metastable excited states of Ar have been demonstrated using both pulsed and CW excitation. In terms of Paschen labeling of the states of Ar, the laser system uses excitation of the 2p9-1s5 transition, and lases on the 2p10-1s5 line. Collisional transfer of population from 2p9 to 2p10 is achieved using He as the buffer gas. For the purpose of modeling and developing this laser, rate constants for state-to-state transfer in Ar(2p(i))+Ar/He mixtures are needed. As the 2p10 level can radiate down to 1s4, this lower level also plays a significant role in the laser kinetics. Consequently, rate constants for the relaxation of 1s4 by Ar and He are also required. In the present study we have used pulsed laser excitation techniques to measure rate constants of relevance to the optically pumped metastable Ar laser.

New laser excitation method for modal analysis of microstructure

A novel impulse laser excitation technique to determine the dynamic response of micro-electro-mechanical systems (MEMS) has been investigated. During the laser excitation experiments, MEMS structures are excited by the wide-band impact force created by the laser–target interaction, and Laser Doppler Vibrometer (LDV) is introduced to measure the vibration velocity of MEMS structures. A distinguishing characteristic of the methodology is that both the excitation and measurement are non-contact, which is especially suitable for the testing of MEMS microstructures that are not easily accessible. This novel excitation method and MEMS modal analysis system are verified by experiments on various cantilever beams. The results show that the laser excitation is capable of exciting the first three modes of cantilevers.

Developing DNA nanotechnology using single-molecule fluorescence.

CONSPECTUS: An important effort in the DNA nanotechnology field is focused on the rational design and manufacture of molecular structures and dynamic devices made of DNA. As is the case for other technologies that deal with manipulation of matter, rational development requires high quality and informative feedback on the building blocks and final products. For DNA nanotechnology such feedback is typically provided by gel electrophoresis, atomic force microscopy (AFM), and transmission electron microscopy (TEM). These analytical tools provide excellent structural information; however, usually they do not provide high-resolution dynamic information. For the development of DNA-made dynamic devices such as machines, motors, robots, and computers this constitutes a major problem. Bulk-fluorescence techniques are capable of providing dynamic information, but because only ensemble averaged information is obtained, the technique may not adequately describe the dynamics in the context of complex DNA devices. The single-molecule fluorescence (SMF) technique offers a unique combination of capabilities that make it an excellent tool for guiding the development of DNA-made devices. The technique has been increasingly used in DNA nanotechnology, especially for the analysis of structure, dynamics, integrity, and operation of DNA-made devices; however, its capabilities are not yet sufficiently familiar to the community. The purpose of this Account is to demonstrate how different SMF tools can be utilized for the development of DNA devices and for structural dynamic investigation of biomolecules in general and DNA molecules in particular. Single-molecule diffusion-based Förster resonance energy transfer and alternating laser excitation (sm-FRET/ALEX) and immobilization-based total internal reflection fluorescence (TIRF) techniques are briefly described and demonstrated. To illustrate the many applications of SMF to DNA nanotechnology, examples of SMF studies of DNA hairpins and Holliday junctions and of the interactions of DNA strands with DNA origami and origami-related devices such as a DNA bipedal motor are provided. These examples demonstrate how SMF can be utilized for measurement of distances and conformational distributions and equilibrium and nonequilibrium kinetics, to monitor structural integrity and operation of DNA devices, and for isolation and investigation of minor subpopulations including malfunctioning and nonreactive devices. Utilization of a flow-cell to achieve measurements of dynamics with increased time resolution and for convenient and efficient operation of DNA devices is discussed briefly. We conclude by summarizing the various benefits provided by SMF for the development of DNA nanotechnology and suggest that the method can significantly assist in the design and manufacture and evaluation of operation of DNA devices.

Experimental and Theoretical Characterization of the 22A′–12A′ Transition of BeOH/D

The hydroxides of Ca, Sr, and Ba are known to be linear molecules, while MgOH is quasilinear. High-level ab initio calculations for BeOH predict a bent equilibrium structure with a bond angle of 140.9°, indicating a significant contribution of covalency to the bonding. However, experimental confirmation of the bent structure is lacking. In the present study, we have used laser excitation techniques to observe the 2(2)A'-1(2)A' transition of BeOH/D in the energy range of 30300-32800 cm(-1). Rotationally resolved spectra were obtained, with sufficient resolution to reveal spin splittings for the electronically excited state. Two-color photoionization was used to determine an ionization energy of 66425(10) cm(-1). Ab initio calculations were used to guide the analysis of the spectroscopic data. Multireference configuration interaction calculations were used to construct potential energy surfaces for the 1(2)A', 2(2)A', and 1(2)A" states. The rovibronic eigenstates supported by these surfaces were determined using the Morse oscillator rigid bender internal dynamics Hamiltonian. The theoretical results were in sufficiently good agreement with the experimental data to permit unambiguous assignment. It was confirmed that the equilibrium geometry of the ground state is bent and that the barrier to linearity lies below the zero-point energies for both BeOH and BeOD.

Evidence of a Cooper minimum in the photoionization from the7s2S1/2excited state of potassium

The existence of a Cooper minimum in the experimentally measured photoionization cross sections for the 7$s$ ${}^{2}$${S}_{1/2}$ excited state of potassium has been reported using a two-step laser excitation technique in conjunction with a time-of-flight mass spectrometer. The photoionization cross sections for the 7$s$ ${}^{2}$${S}_{1/2}$ state have been determined as $(9.78\ifmmode\pm\else\textpm\fi{}0.01)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}2}$, $(3.30\ifmmode\pm\else\textpm\fi{}0.49)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}4},\phantom{\rule{0.16em}{0ex}}(5.47\ifmmode\pm\else\textpm\fi{}0.82)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}3}$, and $(2.06\ifmmode\pm\else\textpm\fi{}0.30)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}2}$ Mb at the ionizing laser wavelengths 1064, 700, 532, and 355 nm, respectively, that validate the presence of a Cooper minimum at \ensuremath{\cong}1.25 eV above the first ionization threshold. The number density has been determined as ${N}_{0}=2\ifmmode\times\else\texttimes\fi{}{10}^{11}$ cm${}^{\ensuremath{-}3}$. The experimentally determined absolute values of the cross sections are in qualitative agreement with the theoretical predictions.

1106 小型スマート複合材の振動制御性能に関する統合最適化とレーザー加振技術による実験的検証(振動・動的応答)

1106 小型スマート複合材の振動制御性能に関する統合最適化とレーザー加振技術による実験的検証(振動・動的応答)

Single-Molecule Three-Color FRET with Both Negligible Spectral Overlap and Long Observation Time

Full understanding of complex biological interactions frequently requires multi-color detection capability in doing single-molecule fluorescence resonance energy transfer (FRET) experiments. Existing single-molecule three-color FRET techniques, however, suffer from severe photobleaching of Alexa 488, or its alternative dyes, and have been limitedly used for kinetics studies. In this work, we developed a single-molecule three-color FRET technique based on the Cy3-Cy5-Cy7 dye trio, thus providing enhanced observation time and improved data quality. Because the absorption spectra of three fluorophores are well separated, real-time monitoring of three FRET efficiencies was possible by incorporating the alternating laser excitation (ALEX) technique both in confocal microscopy and in total-internal-reflection fluorescence (TIRF) microscopy.

Two-color three-photon excitation studies of thallium Rydberg states

We present new data on the even-parity Rydberg states of atomic thallium using two-step three-photon laser excitation technique in conjunction with a thermionic diode ion detector. Atoms are excited from the 6p 2P 1/2 ground state to the 7p 2P 1/2 intermediate state via two-photon excitation and subsequently promoted to the high lying ns 2 S 1/2 and nd 2D 3/2 Rydberg states. The first ionization potential of thallium is determined as 49,266.66(1) cm –1 using data for the ns 2 S 1/2 (25 ≤ n ≤ 54) and nd 2D 3/2 (24 ≤ n ≤ 65) Rydberg series. This value is believed to be more accurate because the contribution due to the hyperfine structure splitting of the 7p 2P 1/2 state (0.07185 cm –1) is much smaller as compared to that of the 6p 2P 1/2 ground state (0.711 cm –1).

Enhancement of Rb fine-structure transfer in ^4He due to three-body collisions

Using ultrafast laser excitation and time-correlated single-photon counting techniques, we have measured the collisional mixing rates between the rubidium 5(2)P fine-structure levels in the presence of (4)He gas. A nonlinear dependence of the mixing rate with (4)He density is observed. We find Rb fine-structure transfer is primarily due to binary collisions at (4)He densities of < or = 10(19) cm(-3), while at greater densities, three-body collisions become significant. We determine a three-body collisional transfer rate coefficient (5(2)P(3/2) --> 5(2)P(1/2)) of 1.25(9)x10(-32) cm(6)/s at 22 degrees C.