Two-dimensional Laser-induced Fluorescence Research Articles

Experimental Investigation of Superheated Liquid Injection in Quiescent and Supersonic Crossflow

This research delves into liquid fuel injection in scramjet combustors, with a focus on the effects of injector length-to-diameter (L/D) ratios and temperatures, spanning from ambient to superheated states. Efficient atomization within the short residence times of liquid-fueled supersonic combustors is crucial for maximizing combustion efficiency. Initial investigations in a quiescent environment aimed to isolate the impact of injector geometry and temperature, utilizing quantitative analysis and diffused backlit illumination to demonstrate that heating fuel beyond its boiling point significantly enhances atomization and dispersion. A notable finding is that higher L/D ratios led to a quicker initiation of flash boiling. Subsequent analyses under supersonic crossflow, using two-dimensional planar laser-induced fluorescence, support these observations. The study further employs spray structure and spatiotemporal characteristic analyses, coefficient of variation, and proper orthogonal decomposition, revealing enhanced flashing atomization at higher L/D ratios. This underscores the critical role of injector design and temperature in optimizing fuel atomization in scramjet engines, highlighting the nuanced interplay between physical injector characteristics and thermal properties in achieving efficient combustion.

Interaction of Cellular Uptake of Nanosilver and Metallothionein Stress Expression Elucidated by 2D Single-Cell Analyses Based on LIF and ICP-MS.

The exploration of cytology mechanisms of nanosilver uptake, toxicity, and detoxification has become an important issue due to its widespread applications. Previous studies have shown differences in the toxic response of mammalian cells to nanosilver. However, the analysis results based on cell populations ignore the impact of cell uptake heterogeneity on the expression of associated stress proteins and cellular physiological activities. In this respect, this work investigated the interaction between silver uptake and metallothionein (MT) expression in individual cells. In addition, we have also preliminarily elucidated the sensitivity variation to AgNPs by using five cell lines, e.g., LX-2, HepG-2, SK-HEP-1, Huh-7, and MDA-MB-231, by adopting a two-dimensional (2D) high-throughput single-cell analysis platform coupling laser-induced fluorescence (LIF) and inductively coupled plasma mass spectrometry (ICP-MS). We developed a 2D data analysis method for one-to-one unification of fluorescence-mass spectrometry signals corresponding to a specific single cell. It indicated that there is no obvious correlation between cellular silver uptake and cell size, and the low MT expression of cells is more sensitive to silver nanoparticles. For each cell line, significant heterogeneity in MT expression was observed. This provides important information for understanding the potential heterogeneous effects of nanosilver on mammalian biological systems. Overall, detoxified cells are more tolerant to nanosilver and normal cells are more tolerant than cancer cells.

Two-dimensional laser-induced fluorescence thermometry in a medium- to high-enthalpy CO2 flow

Ground-based experimental facilities are needed to qualify materials subjected to aerothermodynamic loads during an entry into the Martian atmosphere. In the present work, the focus is on quantifying the temperature field in a medium- to high-enthalpy CO_{2} flow (from 4.5 to {10.5}, hbox {MJ}/hbox {kg}) of a plasma wind tunnel using one- and two-dimensional two-photon absorption laser-induced fluorescence (CO-TALIF) thermometry at a CO number density in the range of 1–2 times 10^{17} cm^{-3}. However, the measurement method developed here can also be used to study satellite propulsion systems. Due to absorption by air, a two-photon excitation scheme of the CO molecule at 115 nm (VUV) was used. Experimental and simulated excitation spectra are compared for temperature determination. For spectrum simulation in the B^1varSigma ^+leftarrow X^1varSigma ^+ system, an existing program was extended and a polynomial regression correlation was developed for signals with low signal-to-noise ratios. After the first one-dimensional temperature measurements using CO-TALIF in the free-stream to quantify the radial temperature profile for three conditions in the medium- to high- enthalpy range, respectively, two-dimensional measurements in a steady state test chamber at room temperature were carried out. For the two-dimensional investigations, a light sheet optic was designed to generate a light sheet free of divergence in width and thickness. The results of the one- and two-dimensional temperature measurements performed at medium- to high-enthalpy conditions provided plausible results concerning both the values and the course in radial and axial direction, the latter being, to the authors’ knowledge, the first two-dimensional temperature measurements under such conditions using CO-TALIF.

Insight into KOH and KCl release behavior of burning wood and straw pellets using quantitative in situ optical measurements

Two-dimensional laser-induced photofragmentation fluorescence (LIPF) was employed to quantitatively visualize the potassium hydroxide (KOH) and potassium chloride (KCl) vapor in the plume above burning wood and straw pellets. In the LIPF measurement, two excitation lasers at 266 and 193 nm were adopted to discriminate KOH and KCl. Meanwhile, tunable diode laser absorption spectroscopy (TDLAS), laser-induced breakdown spectroscopy (LIBS) and two-color pyrometry were used to measure the atomic potassium concentration, total elemental potassium concentration and surface temperature of the burning pellets, respectively. The combustion environment had a temperature of 1550 K and an oxygen concentration of 4.6 vol.%. Two peaks were observed from the temporal potassium release profile of the burning wood, corresponding to the devolatilization and char oxidation stage, while only a single release peak was observed from the burning straw attributed to its high ash content. During the char oxidation and ash cooking stages, KOH was observed to be the dominant potassium species released from the wood, while only KCl was observed for the straw which had a high content of chlorine. About 45% of the total potassium in the wood samples and about 10% in the straw samples were measured to be released during the combustion process. The high content of silicon in the straw retained a considerable amount of potassium in the ash. The wood had the potassium release mainly in the char oxidation stage (∼53% of the total release), while the straw had the main release during the ash cooking stage (∼49% of the total release). During the char oxidation and ash cooking stages, about 32% of Cl was released from the straw pellets in KCl, while the other part of Cl was considered to be released during the devolatilization stage in other Cl species form, such as HCl.

Unpicking vibration-vibration and vibration-torsion interactions in m-fluorotoluene

Two-dimensional laser-induced fluorescence (2D-LIF) spectra are reported for a set of features in the S1 ↔ S0 electronic spectrum of m-fluorotoluene. Two transitions previously assigned to fundamentals are reassigned in the present work. The main reassignments are confirmed with zero-electron-kinetic-energy (ZEKE) spectroscopy. Interactions in the S0, S1 and D0+ electronic states involving vibrational and vibration-torsional (“vibtor”) levels are identified via observed activity. The obtained vibrational wavenumbers compare well to the results of quantum chemical calculations.

Electronic, vibrational, and torsional couplings in N-methylpyrrole: Ground, first excited, and cation states.

The electronic spectrum associated with the S1 ← S0 (Ã1A2←X̃1A1) one-photon transition of jet-cooled N-methylpyrrole is investigated using laser-induced fluorescence (LIF) and (1 + 1) resonance-enhanced multiphoton ionization (REMPI) spectroscopy; in addition, the (2 + 2) REMPI spectrum is considered. Assignment of the observed bands is achieved using a combination of dispersed fluorescence (DF), two-dimensional LIF (2D-LIF), zero-electron-kinetic energy (ZEKE) spectroscopy, and quantum chemical calculations. The spectroscopic studies project the levels of the S1 state onto those of either the S0 state, in DF and 2D-LIF spectroscopy, or the ground state cation (D0 +) state, in ZEKE spectroscopy. The assignments of the spectra provide information on the vibrational, vibration-torsion (vibtor), and torsional levels in those states and those of the S1 levels. The spectra are indicative of vibronic (including torsional) interactions between the S1 state and other excited electronic states, deduced both in terms of the vibrational activity observed and shifts from expected vibrational wavenumbers in the S1 state, attributed to the resulting altered shape of the S1 surface. Many of the ZEKE spectra are consistent with the largely Rydberg nature of the S1 state near the Franck-Condon region; however, there is also some activity that is less straightforward to explain. Comments are made regarding the photodynamics of the S1 state.

Torsions of N-methylpyrrole and its cation

Torsional levels in N-methylpyrrole are investigated in the ground (S0) and first excited (S1) neutral states using two-dimensional laser-induced fluorescence (2D-LIF), and in the ground state cation (D0+) using zero-electron-kinetic-energy (ZEKE) spectroscopy. The ZEKE spectra confirm the largely Rydberg nature of the S1 state. The activity seen in both the 2D-LIF and ZEKE spectra are indicative of vibronic (including torsional) interactions and torsional potentials in the three electronic states are deduced, and are consistent with calculated geometries. The adiabatic ionization energy of N-methylpyrrole is derived as 64250 ± 5 cm−1.

Methyl-torsion-facilitated internal energy delocalization following electronic excitation in m-fluorotoluene: Can meta and para substitution be directly compared?

Coupling between vibrations, and between vibrations and torsions—a generalization of intramolecular vibrational redistribution (IVR)—provides routes to internal energy delocalization, which can stabilize molecules following photoexcitation. Following earlier work on p-fluorotoluene (pFT), this study focuses on m-fluorotoluene (mFT) as probed via the S1 ↔ S0 electronic transitions and the D0+ ← S1 ionization, using two-dimensional laser-induced fluorescence and zero-electron-kinetic energy spectroscopy, respectively. Wavenumbers are reported for a number of vibrations in the S0, S1, and D0+ states and found to compare well to those calculated. In addition, features are seen in the mFT spectra, not commented on in previous studies, which can be assigned to transitions involving vibration–torsion (“vibtor”) levels. Comparisons to the previous work on both m-difluorobenzene and mFT are also made, and some earlier assignments are revised. At lower wavenumbers, well-defined interactions between vibrational and vibtor levels are deduced—termed “restricted IVR,” while at higher wavenumbers, such interactions evolve into more-complicated interactions, moving toward the “statistical IVR” regime. It is then concluded that a comparison between mFT and pFT is less straightforward than implied in earlier studies.

Temporal temperature measurement on burning biomass pellets using phosphor thermometry and two-line atomic fluorescence

We report accurate in-situ optical measurements of surface temperature, volatile gas temperature, and polycyclic aromatic hydrocarbon (PAH) emission over the whole burning history of individual biomass pellets in various combustion atmospheres. Two biomass fuels, wood and straw, were prepared in cylindrical pellets of ∼300 mg. The pellets were burned in a well-controlled combustion atmosphere provided by a laminar flame burner with temperature ranging from 1390 K to 1840 K, and oxygen concentration from zero to 4.5%. The surface temperature of burning biomass pellets was accurately measured, for the first time, using phosphor thermometry, and the volatile gas temperature was measured using two-line atomic fluorescence thermometry. PAH emission was monitored using two-dimensional laser-induced fluorescence. During the devolatilization stage, a relatively low surface temperature, ∼700 K, was observed on the burning pellets. The volatile gas temperature was ∼1100 K and ∼1500 K 5 mm above the top of the pellets in a gas environment of ∼1800 K with 0.5% and 4.5% oxygen, respectively. PAH mainly released when the temperature of the pellet exceeded ∼600 K with the highest concentration close to the surface and being consumed downstream. The weight of the released PAH molecules shifted towards lighter with a reduction of gas environment temperature. The wood and straw pellets had almost the same surface and volatile gas temperature but different compositions in the released volatile gases. The temperature information provided in the present work aids in revealing the reactions in the burning biomass fuels regarding species release, such as various hydrocarbons, nitrogen compounds, and potassium species, and is valuable for further development of biomass thermal conversion models.

Variations in Duschinsky rotations in m-fluorotoluene and m-chlorotoluene during excitation and ionization.

We investigate Duschinsky rotation/mixing between three vibrations for both m-fluorotoluene (mFT) and m-chlorotoluene (mClT), during electronic excitation and ionization. In the case of mFT, we investigate both the S1 → S0 electronic transition and the D0 + ← S1 ionization, by two-dimensional laser-induced fluorescence (2D-LIF) and zero-electron-kinetic energy (ZEKE) spectroscopy, respectively; for mClT, only the D0 + ← S1 ionization was investigated, by ZEKE spectroscopy. The Duschinsky mixings are different in the two molecules, owing to shifts in vibrational wavenumber and variations in the form of the fundamental vibrations between the different electronic states. There is a very unusual behavior for two of the mFT vibrations, where apparently different conclusions for the identity of two S1 vibrations arise from the 2D-LIF and ZEKE spectra. We compare the experimental observations to the calculated Duschinsky matrices, finding that these successfully pick up the key geometric changes associated with each electronic transition and so are successful in qualitatively explaining the vibrational activity in the spectra. Experimental values for a number of vibrations across the S0, S1, and D0 + states are reported and found to compare well to those calculated. Assignments are made for the observed vibration-torsion ("vibtor") bands, and the effect of vibrational motion on the torsional potential is briefly discussed.

Identification of separate isoenergetic routes for vibrational energy flow in p-fluorotoluene.

A deceptively simple feature in the S1 ← S0 spectrum of p-fluorotoluene (pFT), 1013 cm-1 above the origin, is studied using both zero-electron-kinetic-energy (ZEKE) and two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy. It is found to consist of a cornucopia of overlapped transitions to eigenstates that arise from numerous interacting levels. A significant variation in the activity is seen employing both the ZEKE and 2D-LIF techniques. Detailed insight into the complicated spectra can be achieved, owing to the large number of vibrational wavenumbers that have been previously determined for the S0, S1, and D0 + states, summarized herein. It is found that the activity is dominated by two overtones, which are individually interacting with other levels, so providing largely independent routes for vibrational energy flow at the same internal energy. Additionally, other weak features located 900-1050 cm-1 above the origin are examined.

Observation of the onset of torsion-induced, mode-specific dissipative intramolecular vibrational redistribution (IVR)

Evidence is found showing that coupling with vibration-torsion (“vibtor”) levels of both in-plane and out-of-plane vibrations is instrumental in causing dissipative intramolecular vibrational redistribution (IVR). Both zero-electron-kinetic-energy (ZEKE) spectroscopy and two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy are employed to investigate a series of bands located ∼1200 cm−1 above the S1 ← S0 origin in p-fluorotoluene. Transitions in this wavenumber region have been the focus of a number of studies probing IVR. By recording both ZEKE and 2D-LIF spectra, a prepared S1 population is projected onto both the ground state cation and ground state neutral energy states, respectively, giving added confidence to the assignments. The spectral region under discussion is dominated by a pair of fundamental bands, but for the first time, we present explicit evidence that this is complicated by contributions from a number of overtones and combinations, including vibtor levels. We deduce that very different extents of coupling are present across a 60 cm−1 window of the spectrum, even though the density of states is similar; in particular, one of the fundamentals couples efficiently to the increasing bath of levels, while one does not. We explain this by the influence of serendipitous near-coincidences of same-symmetry levels.

Fast 2D Laser-Induced Fluorescence Spectroscopy Mapping of Rare Earth Elements in Rock Samples.

Due to the rapidly increasing use of energy-efficient technologies, the need for complex materials containing rare earth elements (REEs) is steadily growing. The high demand for REEs requires the exploration of new mineral deposits of these valuable elements, as recovery by recycling is still very low. Easy-to-deploy sensor technologies featuring high sensitivity to REEs are required to overcome limitations by traditional techniques, such as X-ray fluorescence. We demonstrate the ability of laser-induced fluorescence (LIF) to detect REEs rapidly in relevant geological samples. We introduce two-dimensional LIF mapping to scan rock samples from two Namibian REE deposits and cross-validate the obtained results by employing mineral liberation analysis (MLA) and hyperspectral imaging (HSI). Technique-specific parameters, such as acquisition speed, spatial resolution, and detection limits, are discussed and compared to established analysis methods. We also focus on the attribution of REE occurrences to mineralogical features, which may be helpful for the further geological interpretation of a deposit. This study sets the basis for the development of a combined mapping sensor for HSI and 2D LIF measurements, which could be used for drill-core logging in REE exploration, as well as in recovery plants.

Complexity surrounding an apparently simple Fermi resonance in p-fluorotoluene revealed using two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy.

Two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy is a powerful tool allowing overlapped features in an electronic spectrum to be separated, and interactions between vibrations and torsions to be identified. Here the technique is employed to assign the 790-825 cm-1 region above the origin of the S1 ← S0 transition in para-fluorotoluene, which provides insight into the unusual time-resolved results of Davies and Reid [Phys. Rev. Lett. 109, 193004 (2012)]. The region is dominated by a pair of bands that arise from a Fermi resonance; however, the assignment is complicated by contributions from a number of overtones and combinations, including vibration-torsion ("vibtor") levels. The activity in the 2D-LIF spectra is compared to the recently reported zero-electron-kinetic-energy spectra [Tuttle et al., J. Chem. Phys. 146, 244310 (2017)] to arrive at a consistent picture of the energy levels in this region of the spectrum.

Unravelling overlaps and torsion-facilitated coupling using two-dimensional laser-induced fluorescence

Two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy is employed to identify contributions to fluorescence excitation spectra that arise from both overlapping bands and coupling between zero-order states (ZOSs). Evidence is found for the role of torsional motion in facilitating the coupling between vibrations that particularly involves the lowest-wavenumber out-of-plane vibrational modes. The experiments are carried out on jet-cooled p-fluorotoluene, where the molecules are initially in the lowest two torsional levels. Here we concentrate on the 390–420 cm−1 features in the S1 ← S0 excitation spectrum, assigning the features seen in the 2D-LIF spectrum, aided by separate dispersed fluorescence spectra. The 2D-LIF spectra allow the overlapping contributions to be cleanly separated, including some that arise from vibrational-torsional coupling. Various coupling routes open up because of the different symmetries of the lowest two torsional modes; these combine with the vibrational symmetry to provide new symmetry-allowed vibration-torsion (‘vibtor’) interactions, and the role of the excited m = 1 torsional level is found to be significant.

Variable-density mixing in turbulent jets with coflow

Two sets of experiments are performed to study variable-density effects in turbulent round jets with coflow at density ratios, $s=4.2$ and $s=1.2$. Ten thousand instantaneous realisations of simultaneous two-dimensional particle image velocimetry and planar laser-induced fluorescence at three axial locations in the momentum-dominated region of the jet allow us to calculate the full turbulent kinetic energy (t.k.e.) budgets, providing insights into the mechanisms of density fluctuation correlations both axially and radially in a non-Boussinesq flow. The strongest variable-density effects are observed within the velocity half-width of the jet, $r_{\tilde{u} _{1/2}}$. Variable-density effects decrease the Reynolds stresses via increased turbulent mass flux in the heavy jet, as shown by previous jet centreline measurements. Radial profiles of turbulent flux show that in the lighter jet t.k.e. is moving away from the centreline, while in the heavy jet it is being transported both inwards towards the centreline and radially outwards. Negative t.k.e. production is observed in the heavy jet, and we demonstrate that this is caused by both reduced gradient stretching in the axial direction and increased turbulent mass fluxes. Large differences in advection are also observed between the two jets. The air jet has higher total advection caused by strong axial components, while density fluctuations in the heavy jet reduce the axial advection significantly. The budget mechanisms in the non-Boussinesq regime are best understood using effective density and velocity half-width, $\unicode[STIX]{x1D70C}_{eff}\bar{u}_{1,CL}^{3}/r_{\tilde{u} _{1/2,eff}}$, a modification of previous scaling.

Direct comparison of two-dimensional and three-dimensional laser-induced fluorescence measurements on highly turbulent flames.

This Letter reports the first direct comparison between two-dimensional (2D) and three-dimensional (3D) laser-induced fluorescence (LIF) applied to highly turbulent flames, with the goal of experimentally illustrating the capabilities and limitations of volumetric LIF (VLIF). To accomplish these goals, planar LIF (PLIF) and VLIF measurements were simultaneously performed on turbulent flames based on the CH radical. The PLIF measurements imaged a planar cross-section of the target flames across a 2D field-of-view (FOV) of 42 mm×42 mm. The VLIF measurements imaged the same region in the target flame with a 3D FOV of 42 mm×42 mm×5 mm, with 5 mm being the thickness of the measurement volume. The VLIF signals generated in this volume were captured by five intensified cameras from different perspectives, based on which a 3D tomographic reconstruction was performed to obtain the 3D reconstruction of the CH radical (as a marker of the flame front). The PLIF measurements were then compared to a cross-section of the VLIF measurement to demonstrate the feasibility and accuracy of instantaneous 3D imaging of flame topography and flame surface area in highly turbulent flames.

Laser-induced fluorescence analysis of plasmas for epitaxial growth of YBiO3 films with pulsed laser deposition

We record the two-dimensional laser-induced fluorescence (LIF) on multiple plasma constituents in a YBiO3 plasma. This allows us to directly link the influence of oxygen present in the background gas during pulsed laser deposition to the oxidation of plasma species as well as the formation of epitaxial YBiO3 films. With spatiotemporal LIF mapping of the plasma species (Y, YO, Bi, and BiO) in different background gas compositions, we find that little direct chemical interaction takes place between the plasma plume constituents and the background gas. However, a strong influence of the background gas composition can be seen on the YBO film growth, as well as a strong correlation between the oxygen fraction in the background gas and the amount of YO in the plasma plume. We assign this correlation to a direct interaction between the background gas and the target in between ablation pulses. In an O2 background, an oxygen-rich surface layer forms in between ablation pulses, which provides additional oxygen for the plasma plume during target ablation. This differs from our previous observations in STO and LAO plasmas, where species oxidation primarily takes place during propagation of the plasma plume towards the substrate.

Two-dimensional fluorescence spectroscopy of laser-produced plasmas.

We use a two-dimensional laser-induced fluorescence spectroscopy technique to measure the coupled absorption and emission properties of atomic species in plasmas produced via laser ablation of a solid aluminum target at atmospheric pressure. Emission spectra from the Al I 394.4nm and Al I 396.15nm transitions are measured while a frequency-doubled, continuous wave (cw) Ti:sapphire laser is tuned across the Al I 396.15nm transition. The resulting two-dimensional spectra show the energy coupling between the two transitions via increased emission intensity for both transitions during resonant absorption of the cw laser at one transition. Time-delayed, gated detection of the emission spectrum is used to isolate resonantly excited fluorescence emission from thermally excited emission from the plasma. In addition, the tunable cw laser measures the absorption spectrum of the Al transition with ultrahigh resolution after the plasma has cooled, resulting in narrower spectral linewidths than observed in emission spectra. Our results highlight that fluorescence spectroscopy employing cw laser re-excitation after pulsed laser ablation combines benefits of both traditional emission and absorption spectroscopic methods.

Detection of the Thorium Dimer via Two-Dimensional Fluorescence Spectroscopy.

Thorium dimer, Th2, has been detected in the gas phase via two-dimensional laser-induced fluorescence electronic spectroscopy. The visible excitation spectra are broad, unstructured features with an approximate line width of 10 cm(-1). The spectrum consists of vibrational progressions associated with excitation from the ground electronic state to two different excited electronic states. The dispersed fluorescence was analyzed to give ground state vibrational constants ωe = 134.86 ± 0.66 cm(-1) and ωexe = 0.50 ± 0.04 cm(-1). Vibrational constants ωe = 169 ± 3 and 212 ± 2 cm(-1) were determined for the two excited electronic states. The radiative lifetimes were measured. A comparison with theoretical predictions is given.