Raman Loss Spectroscopy Research Articles

Enhanced gas‐phase nucleation of diamond nanoparticles in a microplasma torch

AbstractIn this work, we present and characterize a microwave plasma microtorch that can support the formation of diamond nanoparticles (DNPs) in the gas phase when using hydrogen‐methane as a precursor gas. We first showed how the nonequilibrium character of the plasma obtained in this microtorch ensures enhanced H‐atom, , and production at moderate gas temperature levels that provides thermal stability of DNPs. The material characterization by TEM, Raman, and electron energy loss spectroscopy spectra confirm the presence of a substantial amount of diamond phase in the carbon dust particles collected from the plasma phase. Investigation of the effects of injected microwave power on the process characteristics showed a direct correlation between enhanced production and the appearance of the diamond phase, which points out the critical role of as far as gas‐phase nucleation of DNPs is concerned.

Excited‐State Intramolecular Charge‐Transfer Dynamics in 4‐Dimethylamino‐4′‐cyanodiphenylacetylene: An Ultrafast Raman Loss Spectroscopic Perspective

AbstractPhoto‐initiated intramolecular charge transfer (ICT) processes play a pivotal role in the excited state reaction dynamics in donor‐bridge‐acceptor systems. The efficacy of such a process can be improved by modifying the extent of π‐conjugation, relative orientation/twists of the donor/acceptor entities and polarity of the environment. Herein, 4‐dimethylamino‐4′‐cyanodiphenylacetylene (DACN‐DPA), a typical donor‐π‐bridge‐acceptor system, was chosen to unravel the role of various internal coordinates that govern the extent of photo‐initiated ICT dynamics. Transient absorption (TA) spectra of DACN‐DPA in n‐hexane exhibit a lifetime of >2 ns indicating the formation of a triplet state while, in acetonitrile, a short time‐constant of ∼2 ps indicates the formation of charge transferred species. Ultrafast Raman loss spectroscopy (URLS) measurements show distinct temporal and spectral dynamics of Raman bands associated with C≡C and C=C stretching vibrations. The appearance of a new band at ∼1492 cm−1 in acetonitrile clearly indicates structural modification during the ultrafast ICT process. Furthermore, these observations are supported by TD‐DFT computations.

Mechanisms of fault mirror formation and fault healing in carbonate rocks

Abstract The development of smooth, mirror-like surfaces provides insight into the mechanical behaviour of crustal faults during the seismic cycle. To determine the thermo-chemical mechanisms of fault mirror formation, we investigated carbonate fault systems in seismically active areas of central Greece. Using multi-scale electron microscopy combined with Raman and electron energy loss spectroscopy, we show that fault mirror surfaces do not always develop from nanogranular volumes. The microstructural observations indicate that decarbonation is the transformation process that leads to the formation of smooth surface coatings in the faults studied here. Piercement structures on top of the fault surfaces indicate calcite decarbonation, producing CO2 and lime (CaO). Lime subsequently reacts to portlandite (Ca(OH)2) under hydrous conditions. Nanoscale imaging and electron diffraction reveal a thin coating of a non-crystalline material sporadically mixed with nano-clay, forming a complex-composite material that smooths the slip surface. Spectroscopic analyses reveal that the thin coating is non-crystalline carbon. We suggest that ordering (hybridisation) of amorphous carbon led to the formation of partly-hybridised amorphous carbon but did not reach full graphitisation. Calcite nanograins, 100 nm) and new nanograins formed by back-reaction (secondary nanograins,

Unraveling structural dynamics in isoenergetic excited S1 and multi-excitonic 1(TT) states of 9,10-bis(phenylethynyl)anthracene (BPEA) in solution via ultrafast Raman loss spectroscopy.

Polyacenes, such as anthracene, tetracene, pentacene etc., have been identified as potential candidates for singlet fission (SF) and triplet-triplet annihilation (TTA) processes in their crystalline and thin film forms as they possess significant singlet and triplet exciton couplings. Interestingly, phenyl-ethynyl substitution to anthracene at the 9,10 positions (9,10-bis(phenylethynyl)anthracene/BPEA) enhances the transverse π-electron conjugation and retains the planar structure even in the excited state. The excited singlet state S1 and the multi-excitonic state 1(TT) in BPEA are separated by ∼30 meV (∼250 cm-1) making it an ideal system for both SF and TTA applications. BPEA is very effective in photon up-conversion even for low input intensities. Transient absorption measurements of BPEA in n-hexane solution are inadequate for distinguishing the S1 state and the multi-excitonic state 1(TT), since the spectroscopic features are complex (mixed) due to the isoenergetic nature and the existence of an equilibrium between these states. However, ultrafast Raman loss spectroscopy reveals a systematic red shift and a blue shift in the central frequencies of the Raman modes corresponding to C[double bond, length as m-dash]C and C[triple bond, length as m-dash]C vibrational frequencies with time constants of ∼2.0 and ∼20 ps, respectively. Such a shift in the Raman frequencies is direct evidence of the structural changes that take place while changing from excited singlet state S1 to the multi-excitonic state on the potential surface.

Excited state structural dynamics of 4-cyano-4'-hydroxystilbene: deciphering the signatures of proton-coupled electron transfer using ultrafast Raman loss spectroscopy.

The photo-initiated proton-coupled electron transfer (PCET) process plays a crucial role in the context of light harvesting in various biological and chemical systems. Molecular model systems are typically employed to understand the mechanisms underlying the functioning of complex biological systems. Some molecular dyads based on the PCET property have been particularly designed to achieve efficient sunlight-to-fuel production. Organic photoacids are potential sources for such applications since they exhibit an enhancement in their acidity upon photoexcitation, facilitating the mimicking of some of the biological processes. p-Hydroxybenzylideneimidazolinone (p-HBI), an organic photoacid, is a key chromophore in green fluorescent protein, which exhibits green emission due to excited state proton transfer. Herein, we investigate the structural changes and dynamics of 4-cyano-4'-hydroxystilbene (CHSB), an analogue of p-HBI, in the presence of an external base, t-butylamine (TBA), using the techniques of ultrafast transient absorption, emission and ultrafast Raman loss spectroscopy. Femtosecond fluorescence up-conversion measurements of the CHSB-TBA adduct reveal a precursor-successor relationship between the ∼420 and ∼530 nm emission bands, which implies that the adduct evolves predominantly through an electron-proton transferred state. Further, Raman measurements show a clear distinction in the dynamics of the C[double bond, length as m-dash]C stretch of CHSB in the presence and absence of TBA in terms of the amplitude growth (0.45 ps vs. instantaneous) and the central frequency (1584 vs. 1523 cm-1).

Probing the effect of solvation on photoexcited 2-(2'-hydroxyphenyl)benzothiazole via ultrafast Raman loss spectroscopic studies.

2-(2'-Hydroxyphenyl)benzothiazole (HBT) molecule is known to exhibit efficient excited state intramolecular proton transfer. As a consequence, it shows fluorescence with a large Stokes shift (∼10 000 cm-1) in non-polar solvents. However, fluorescence in polar solvents has a dual-band which corresponds to the emission from both the enol* and the keto* forms. Also, the excited state lifetime significantly varies with the solvent polarity. Recently, Mohammed et al. [J. Phys. Chem. A 115, 7550 (2011)] have shown that the excited state of HBT in acetonitrile (ACN) relaxes back to its ground electronic state through two competitive decay pathways, i.e., intramolecular proton transfer and intramolecular twisting between hydroxyphenyl and benzothiazole units in contrast to its behavior when it is in tetrachloroethene, a non-polar solvent. Here, by following the time-evolution of vibrational features of excited state HBT in ACN through ultrafast Raman loss spectroscopy, we demonstrate a direct evidence for the involvement of torsional motion leading to an ultrashort lifetime of HBT. The time evolution of the C7-N vibrational frequency exhibited a red-shift in its peak position, clearly indicating the evolution of the initially planar cis-keto* form to the more twisted keto* form. Density functional theory calculations also well corroborate the experimental findings. Furthermore, wavepacket analysis of this mode reveals a strong correlation with the torsional motion in ACN.

Ultrafast Raman Loss Spectroscopy Unravels the Dynamics in Entangled Singlet and Triplet States in Thioxanthone.

Thioxanthone (TX), an aromatic ketone, exhibits significant solvent-dependent photophysical properties. Herein, we employed time-resolved ultrafast Raman loss spectroscopy (URLS) to decipher the solvent-dependent structural dynamics in entangled singlet and triplet states of photoexcited TX. The evolution of the vibrational spectrum reveals structural changes that occur during the intersystem-crossing (ISC) process and the subsequent energy dissipation to the surrounding solvent. The C═O stretch (∼1320 cm-1) of TX in the excited state acts as the marker band as it undergoes a red shift with time constants of ∼45 and ∼5 ps in acetonitrile and methanol, respectively. Such a red shift is an indicator of the softening of the bond due to the change in the electronic spin states. We also observed a blue shift in Raman frequencies corresponding to the C═C stretch and the C═O stretching modes of TX in acetonitrile and methanol, indicating vibrational cooling in the excited singlet and triplet states. In the case of TX in cyclohexane, vibrational modes at 190 and 415 cm-1 exhibit a blue shift with a time constant of ∼700 fs, which represents the structural distortion during internal conversion (S2 → S1) process. The kinetics of amplitudes of these modes follows biexponential growth with time constants of ∼3 and ∼14 ps representing the time scales for the ISC process and the planarization process in the triplet state, respectively. The URLS study therefore provides a direct measure of the various stages of the solvent-dependent structural dynamics in the excited state of TX.

Femtosecond coherent nuclear dynamics of excited tetraphenylethylene: Ultrafast transient absorption and ultrafast Raman loss spectroscopic studies.

Ultrafast torsional dynamics plays an important role in the photoinduced excited state dynamics. Tetraphenylethylene (TPE), a model system for the molecular motor, executes interesting torsional dynamics upon photoexcitation. The photoreaction of TPE involves ultrafast internal conversion via a nearly planar intermediate state (relaxed state) that further leads to a twisted zwitterionic state. Here, we report the photoinduced structural dynamics of excited TPE during the course of photoisomerization in the condensed phase by ultrafast Raman loss (URLS) and femtosecond transient absorption (TA) spectroscopy. TA measurements on the S1 state reveal step-wise population relaxation from the Franck-Condon (FC) state → relaxed state → twisted state, while the URLS study provides insights on the vibrational dynamics during the course of the reaction. The TA spectral dynamics and vibrational Raman amplitudes within 1 ps reveal vibrational wave packet propagating from the FC state to the relaxed state. Fourier transformation of this oscillation leads to a ∼130 cm-1 low-frequency phenyl torsional mode. Two vibrational marker bands, Cet=Cet stretching (∼1512 cm-1) and Cph=Cph stretching (∼1584 cm-1) modes, appear immediately after photoexcitation in the URLS spectra. The initial red-shift of the Cph=Cph stretching mode with a time constant of ∼400 fs (in butyronitrile) is assigned to the rate of planarization of excited TPE. In addition, the Cet=Cet stretching mode shows initial blue-shift within 1 ps followed by frequency red-shift, suggesting that on the sub-picosecond time scale, structural relaxation is dominated by phenyl torsion rather than the central Cet=Cet twist. Furthermore, the effect of the solvent on the structural dynamics is discussed in the context of ultrafast nuclear dynamics and solute-solvent coupling.

Quantitative Determination of the Differential Raman Scattering Cross Sections of Glucose by Femtosecond Stimulated Raman Scattering.

Femtosecond stimulated Raman spectroscopy (FSRS) is a vibrational spectroscopy technique that has been used in a wide variety of applications: from transient vibrational signature tracking to amplifying weak normal Raman scattering signals. Presented here is an application of FSRS to quantify the differential Raman scattering cross sections (DRSCs) of glucose. In using FSRS to determine the DRSCs of multiple glucose vibrational modes, we demonstrate the applicability of both stimulated Raman loss (SRL) spectroscopy and stimulated Raman gain (SRG) FSRS. Using the two analogous FSRS techniques, SRG and SRL, we determine that the DRSCs of glucose excited at 514.5 nm range from a low of 5.0 ± 1.1 × 10-30 to a high of 8.9 ± 0.9 × 10-30 cm2 molecule-1 sr-1. This work establishes both the compatibility of SRL for measuring DRSCs and values for the DRSC of multiple vibrational modes of glucose.

Mode specific excited state dynamics study of bis(phenylethynyl)benzene from ultrafast Raman loss spectroscopy.

Femtosecond transient absorption (fs-TA) and Ultrafast Raman Loss Spectroscopy (URLS) have been applied to reveal the excited state dynamics of bis(phenylethynyl)benzene (BPEB), a model system for one-dimensional molecular wires that have numerous applications in opto-electronics. It is known from the literature that in the ground state BPEB has a low torsional barrier, resulting in a mixed population of rotamers in solution at room temperature. For the excited state this torsional barrier had been calculated to be much higher. Our femtosecond TA measurements show a multi-exponential behaviour, related to the complex structural dynamics in the excited electronic state. Time-resolved, excited state URLS studies in different solvents reveal mode-dependent kinetics and picosecond vibrational relaxation dynamics of high frequency vibrations. After excitation, a gradual increase in intensity is observed for all Raman bands, which reflects the structural reorganization of Franck-Condon excited, non-planar rotamers to a planar conformation. It is argued that this excited state planarization is also responsible for its high fluorescence quantum yield. The time dependent peak positions of high frequency vibrations provide additional information: a rapid, sub-picosecond decrease in peak frequency, followed by a slower increase, indicates the extent of conjugation during different phases of excited state relaxation. The CC triple (-C≡C-) bond responds somewhat faster to structural reorganization than the CC double (>C=C<) bonds. This study deepens our understanding of the excited state of BPEB and analogous linear pi-conjugated systems and may thus contribute to the advancement of polymeric "molecular wires."

Inelastic light and electron scattering in parabolic quantum dots in magnetic field: Implications of generalized Kohn's theorem

We investigate a one-component, quasi–zero-dimensional, quantum plasma exposed to a parabolic potential and an applied magnetic field in the symmetric gauge. If the size of such a system as can be realized in the semiconducting quantum dots is on the order of the de Broglie wavelength, the electronic and optical properties become highly tunable. Then the quantum size effects challenge the observation of many-particle phenomena such as the magneto-optical absorption, Raman intensity, and electron energy loss spectrum. An exact analytical solution of the problem leads us to infer that these many-particle phenomena are, in fact, dictated by the generalized Kohn's theorem in the long-wavelength limit. Maneuvering the confinement and/or the magnetic field furnishes the resonance energy capable of being explored with the FIR, Raman, or electron energy loss spectroscopy. This implies that either of these probes should be competent in observing the localized magnetoplasmons in the system. A deeper insight into the physics of quantum dots is paving the way for their implementation in diverse fields such as quantum computing and medical imaging.

Novel growth of carbon nanotubes on nickel nanowires

Abstract A novel growth phenomenon is presented in this paper where carbon nanotubes (CNT) were grown successfully on nickel (Ni) nanowire using chemical vapour deposition technique. The decomposed carbon from ethylene diffused through the surface of nanowires and precipitated into hollow cylindrical carbon structures. Nanotubes of various lengths are found to have grown along the length of the outer side of the nanowires and were firmly rooted to their walls. The presence of a thin layer of oxide (~ 3 nm) on the top surface of nanowires is believed to have promoted the growth of CNT. Raman, X-ray photoelectron (XPS) and electron energy loss spectroscopy (EELS) were conducted in order to understand the formation of nanotubes and verify their presence, their level of crystallinity and chemical bonding structure with nanowires. This hybrid nanostructure is also found to have ferromagnetic behaviour, which can be applied in devices such as magnetic sensors and spintronic devices that combine the unique properties of CNT and Ni nanowires.

Screening properties and plasmons of Hg(Cd)Te quantum wells

Under certain conditions, Hg(Cd)Te quantum wells (QWs) are known to realize a time-reversal symmetric, two-dimensional topological insulator phase. Its low-energy excitations are well-described by the phenomenological Bernevig-Hughes-Zhang (BHZ) model that interpolates between Schr\"odinger and Dirac fermion physics. We study the polarization function of this model in random phase approximation (RPA) in the intrinsic limit and at finite doping. While the polarization properties in RPA of Dirac and Schr\"odinger particles are two comprehensively studied problems, our analysis of the BHZ model bridges the gap between these two limits, shedding light on systems with intermediate properties. We gain insight into the screening properties of the system and on its characteristic plasma oscillations. Interestingly, we discover two different kinds of plasmons that are related to the presence of intra- and interband excitations. Observable signatures of these plasmons are carefully analyzed in a variety of distinct parameter regimes, including the experimentally relevant ones for Hg(Cd)Te QWs. We conclude that the discovered plasmons are observable by Raman or electron loss spectroscopy.

Charge Doping of Large-Area Graphene by Gold-Alloy Nanoparticles

We present a facile, one-step, and surfactant-free method for direct synthesis and loading of stable gold and gold-alloy nanoparticles (NPs) on large-area graphene using an electrical discharge in a liquid environment, termed solution plasma. We observed a charge doping of graphene by the gold NPs, which depends on the particles’ chemical composition, even if the NPs contain a few percent of trivalent sp metals, such as indium (In) or gallium (Ga). Raman and electron energy loss spectroscopy (EELS) methods show that graphene is doped with electrons (n-type) in the case of gold NPs and with holes (p-type) in the case of gold-alloy NPs. The Raman band shift indicates that the amount of the transferred electrons from the gold NPs to graphene is −2 × 10–4 electrons per unit cell. The gold-alloy NPs receive from graphene (2 and 4) × 10–5 electrons per unit cell if the gold NPs contain In and Ga, respectively. In the EELS spectra, the decrease in the intensity of the 1s-π* transition and the shift of the π* pea...

One dimensionality and spectroscopy in carbon nanotubes

Unlike regular three-dimensional solids two of a nanotube dimensions are confined and quantized. Bulk samples consist of irregular networks of merging and splitting bundles of parallel tubes. On a local scale, nanotubes are at the same time one-dimensional crystals and two-dimensional quantum rings. They have attracted extensive studies on individual aspects in their electronic and optical properties [1]. The current contribution aims at bridging the fundamental physical concepts behind carbon nanotubes to their unique spectroscopic signatures in optical absorption, luminescence, Raman and electron energy loss spectroscopy. The aim is not to compete with the local depth of a focused review, but to briefly convey the physical concept and related spectroscopic signatures of one-dimensionality. Indirect signatures are the manifold appearances of van Hove singularities in their optical transitions. Direct probes of one-dimensionality unveil the confined momentum space, which manifests in the distinction of localized and propagating excitations.

Resonant stimulated Raman gain and loss spectroscopy in Rb atomic vapor

Based on our experimental observations of the resonant stimulated Raman gain and loss spectra in Rb atomic vapor, we propose an alternative interpretation of electromagnetically induced transparency (EIT). We find that, in the presence of a coupling field, a probe beam can exhibit both gain and loss depending on the frequencies of the incident beams. The gain and loss can coexist in a Doppler-broadened system, leading to polarization interference between atoms of different velocities, with a sharp transition from gain to loss as the probe-field frequency is scanned. We use the concept of Raman gain, instead of the commonly accepted quantum Fano interference, to explain the phenomenon of EIT and its transparency window as being due to the suppression of linear absorption by the Raman gain. Using this concept, the phenomena of EIT and Autler-Townes splitting may be explained within the same framework.

Basic principles of ultrafast Raman loss spectroscopy#

When a light beam passes through any medium, the effects of interaction of light with the material depend on the field intensity. At low light intensities the response of materials remain linear to the amplitude of the applied electromagnetic field. But for sufficiently high intensities, the optical properties of materials are no longer linear to the amplitude of applied electromagnetic field. In such cases, the interaction of light waves with matter can result in the generation of new frequencies due to nonlinear processes such as higher harmonic generation and mixing of incident fields. One such nonlinear process, namely, the third order nonlinear spectroscopy has become a popular tool to study molecular structure. Thus, the spectroscopy based on the third order optical nonlinearity called stimulated Raman spectroscopy (SRS) is a tool to extract the structural and dynamical information about a molecular system. Ultrafast Raman loss spectroscopy (URLS) is analogous to SRS but is more sensitive than SRS. In this paper, we present the theoretical basis of SRS (URLS) techniques which have been developed in our laboratory.

Inverse Raman bands in ultrafast Raman loss spectroscopy

Ultrafast Raman loss spectroscopy (URLS) is equivalent to anti-Stokes femtosecond stimulated Raman spectroscopy (FSRS), using a broadband probe pulse that extends to the blue of the narrow bandwidth Raman pump, and can be described as inverse Raman scattering (IRS). Using the Feynman dual time-line diagram, the third-order polarization for IRS with finite pulses can be written down in terms of a four-time correlation function. An analytic expression is obtained for the latter in the harmonic approximation which facilitates computation. We simulated the URLS of crystal violet (CV) for various resonance Raman pump excitation wavelengths using the IRS polarization expression with finite pulses. The calculated results agreed well with the experimental results of S. Umapathy et al., J. Chem. Phys. 133, 024505 (2010). In the limit of monochromatic Raman pump and probe pulses, we obtain the third-order susceptibility for multi-modes, and for a single mode we recover the well-known expression for the third-order susceptibility, χ(IRS) ((3)), for IRS. The latter is used to understand the mode dependent phase changes as a function of Raman pump excitation in the URLS of CV.

Ultrafast Raman loss spectroscopy (URLS): instrumentation and principle

AbstractIn this paper, we report on the concept and the design principle of ultrafast Raman loss spectroscopy (URLS) as a structure‐elucidating tool. URLS is an analogue of stimulated Raman scattering (SRS) but more sensitive than SRS with better signal‐to‐noise ratio. It involves the interaction of two laser sources, namely, a picosecond (ps) Raman pump pulse and a white‐light (WL) continuum, with a sample, leading to the generation of loss signals on the higher energy (blue) side with respect to the wavelength of the Raman pump unlike the gain signal observed on the lower energy (red) side in SRS. These loss signals are at least 1.5 times more intense than the SRS signals. An experimental study providing an insight into the origin of this extra intensity in URLS as compared to SRS is reported. Furthermore, the very requirement of the experimental protocol for the signal detection to be on the higher energy side by design eliminates the interference from fluorescence, which appears on the red side. Unlike CARS, URLS signals are not precluded by the non‐resonant background and, being a self‐phase‐matched process, URLS is experimentally easier. Copyright © 2011 John Wiley &amp; Sons, Ltd.

Mode-dependent dispersion in Raman line shapes: Observation and implications from ultrafast Raman loss spectroscopy

Ultrafast Raman loss spectroscopy (URLS) enables one to obtain the vibrational structural information of molecular systems including fluorescent materials. URLS, a nonlinear process analog to stimulated Raman gain, involves a narrow bandwidth picosecond Raman pump pulse and a femtosecond broadband white light continuum. Under nonresonant condition, the Raman response appears as a negative (loss) signal, whereas, on resonance with the electronic transition the line shape changes from a negative to a positive through a dispersive form. The intensities observed and thus, the Franck-Condon activity (coordinate dependent), are sensitive to the wavelength of the white light corresponding to a particular Raman frequency with respect to the Raman pump pulse wavelength, i.e., there is a mode-dependent response in URLS.