Impulsive Stimulated Raman Scattering Research Articles

Attosecond Probing of Coherent Vibrational Dynamics in CBr4.

A coherent vibrational wavepacket is launched and manipulated in the symmetric stretch (a1) mode of CBr4, by impulsive stimulated Raman scattering (ISRS) from nonresonant 400 nm laser pump pulses with various peak intensities on the order of tens of 1012 W/cm2. Extreme ultraviolet (XUV) attosecond transient absorption spectroscopy (ATAS) records the wavepacket dynamics as temporal oscillations in XUV absorption energy at the bromine M4,5 3d3/2,5/2 edges around 70 eV. The results are augmented by nuclear time-dependent Schrödinger equation simulations. Slopes of the (Br 3d3/2,5/2)-110a1* core-excited state potential energy surface (PES) along the a1 mode are calculated to be -9.4 eV/Å from restricted open-shell Kohn-Sham calculations. Using analytical relations derived for the small-displacement limit and the calculated slopes of the core-excited state PES, a deeper insight into the vibrational dynamics is obtained by retrieving the experimental excursion amplitude of the vibrational wavepacket and the amount of population transferred to the vibrational first-excited state as a function of pump-pulse peak intensity. Experimentally, the results show that XUV ATAS is capable of resolving oscillations in the XUV absorption energy on the order of a few to tens of meV with tens of femtosecond time precision. This corresponds to change in C-Br bond length on the order of 10-4 to 10-3 Å. The results and the analytic relationships offer a clear physical picture, on multiple levels of understanding, of how the pump-pulse peak intensity controls the vibrational dynamics launched by nonresonant ISRS in the small-displacement limit.

Stimulated Raman blockade in coherent phonon generation

We theoretically investigate the behavior of coherent optical phonons in an electron–phonon coupled system at moderate laser intensity: below GW/cm2. We calculate the coherent phonons from impulsive stimulated Raman scattering (ISRS) and impulsive absorption (IA) mechanisms with a nonperturbative model. The generation efficiency of coherent phonons in single-pulse excitation exhibits gradual nonlinear saturation with increasing optical intensity in a nonperturbative regime. The ISRS mechanism exhibits substantial saturation at relatively low pulse intensity, whereas the IA mechanism remains roughly linear. We further examine the influence of double-pulse excitation on quantum path interference. The ISRS mechanism exhibits a pronounced saturation effect near 0 fs of pump–pump delay, whereas the IA process exhibits negligible saturation behavior. These results reproduce well experimental data obtained by double-pulse excitation and support our proposal that ISRS is the primary quantum path for the observed coherent phonons in gallium arsenide.

Selective Detection in Impulsive Low-Frequency Raman Imaging Using Shaped Probe Pulses

Impulsive stimulated Raman scattering (ISRS) using a single short femtosecond pump pulse to excite molecular vibrations offers an elegant pump-probe approach to perform vibrational imaging below $200\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$. One shortcoming of ISRS is its inability to offer vibrational selectivity as all the vibrational bonds whose frequencies lie within the short pump-pulse bandwidth are excited. To date, several coherent control techniques have been explored to address this issue and selectively excite a specific molecular vibration by shaping the pump pulse. There has not been any systematic work that reports an analogous shaping of the probe pulse to implement preferential detection. In this work, we focus on vibrational imaging and report vibrational selective detection by shaping the probe pulse in time. We demonstrate numerically and experimentally two pulse-shaping strategies with one functioning as a vibrational notch filter and the other functioning as a vibrational low-pass filter. This enables fast ($25\phantom{\rule{0.2em}{0ex}}\text{\ensuremath{\mu}}\mathrm{s}/$pixel) and selective hyperspectral imaging in the low-frequency regime ($<200\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$).

Anharmonic Exciton‐Phonon Coupling in Metal‐Organic Chalcogenides Hybrid Quantum Wells

AbstractIn contrast to inorganic quantum wells, hybrid quantum wells (HQWs) based on metal‐organic semiconductors are characterized by relatively soft lattices, in which excitonic states can strongly couple to lattice phonons. Therefore, understanding the lattice's impact on exciton dynamics is essential for harnessing the optoelectronic potential of HQWs. Beyond 2D metal halide perovskites, layered metal‐organic chalcogenides (MOCs), which are an air‐stable, underexplored material class hosting room‐temperature excitons, can be exploited as photodetectors, light emitting devices, and ultrafast photoswitches. Here, the role of phonons in the optical transitions of the prototypical MOC [AgSePh]∞ is elucidated. Impulsive stimulated Raman scattering (ISRS) allows the detection of coherent exciton oscillations driven by Fröhlich interaction with low‐energy optical phonons. Steady state absorption and Raman spectroscopies reveal a strong exciton‐phonon coupling (Huang‐Rhys parameter ≈1.7) and its anharmonicity, manifested as a nontrivial temperature‐dependent Stokes shift. The ab initio calculations support these observations, hinting at an anharmonic behavior of the low‐energy phonons <200 cm−1. These results untangle complex exciton‐phonon interactions in MOCs, establishing an ideal testbed for room‐temperature many‐body phenomena.

Element- and enantiomer-selective visualization of molecular motion in real-time

Ultrafast optical-domain spectroscopies allow to monitor in real time the motion of nuclei in molecules. Achieving element-selectivity had to await the advent of time resolved X-ray spectroscopy, which is now commonly carried at X-ray free electron lasers. However, detecting light element that are commonly encountered in organic molecules, remained elusive due to the need to work under vacuum. Here, we present an impulsive stimulated Raman scattering (ISRS) pump/carbon K-edge absorption probe investigation, which allowed observation of the low-frequency vibrational modes involving specific selected carbon atoms in the Ibuprofen RS dimer. Remarkably, by controlling the probe light polarization we can preferentially access the enantiomer of the dimer to which the carbon atoms belong.

Nearly degenerate two-color impulsive coherent Raman hyperspectral imaging.

Impulsive stimulated Raman scattering (ISRS) is a robust technique for studying low frequency (<300cm-1) Raman vibrational modes, but ISRS has faced difficulty in translation to an imaging modality. A primary challenge is the separation of the pump and probe pulses. Here we introduce and demonstrate a simple strategy for ISRS spectroscopy and hyperspectral imaging that uses complementary steep edge spectral filters to separate the probe beam detection from the pump and enables simple ISRS microscopy with a single-color ultrafast laser source. ISRS spectra are obtained that span from the fingerprint region down to <50cm-1 vibrational modes. Hyperspectral imaging and polarization-dependent Raman spectra are also demonstrated.

Study of Impulsive Stimulated Raman Scattering Effects Using the Femtosecond Pump–Probe Z-Scan Technique

Impulsive stimulated Raman scattering (ISRS) is a nonlinear pump–probe spectroscopy technique particularly suitable to study vibrational intermolecular and intramolecular modes in complex systems. For the latter, recent studies of ISRS microscopy with low-energy laser sources have attracted attention for investigation of photosensitive or biological samples. Following this stream of interest, in this paper, we report an investigation on the relationship between femtosecond ISRS data and pump–probe Z-scan measurements, showing that the latter technique is capable of capturing the Kerr nonlinearities induced by the molecular vibrational modes. To this aim, firstly, spectrally filtered and Raman-induced Kerr ISRS signals were simultaneously acquired to determine the sample nonlinear response and to establish the reference data for the Z-scan analysis. Then, by adopting a suitable experimental arrangement to avoid thermo-optical effects, we were able to unambiguously observe the Raman-induced effects in Z-scan measurements, thus obtaining a consistent picture between ISRS and Z-scan for the first time, to the best of our knowledge. Practical applications of the proposed method include calibrated measurements of the contribution of the internal (Raman) and external molecular modes to the nonlinear refractive index.

Broadband Impulsive Stimulated Raman Scattering Based on a Chirped Detection.

In impulsive stimulated Raman scattering, vibrational oscillations, coherently stimulated by a femtosecond Raman pulse, are monitored in real time and read out as intensity modulations in the transmission of a temporally delayed probe pulse. Critically, in order to retrieve broadband Raman spectra, a fine sampling of the time delays between the Raman and probe pulses is required, making conventional ISRS ineffective for probing irreversible phenomena and/or weak scatterers typically demanding long acquisition times, with signal-to-noise ratios that crucially depend on the pulse fluences and overlap stabilities. To overcome such limitations, here we introduce the chirped-based impulsive stimulated raman scattering (CISRS) technique. Specifically, we show how introducing a chirp in the probe pulse can be exploited for recording the Raman information without the need to scan over the Raman-probe pulse delay. We then experimentally demonstrate with a few examples how to use the introduced scheme to measure Raman spectra.

Quantum model for impulsive stimulated Raman scattering

The interaction between ultrashort light pulses and non-absorbing materials is dominated by impulsive stimulated Raman scattering (ISRS). The description of ISRS in the context of pump&probe experiments is based on effective classical models describing the interaction between the phonon and pulsed electromagnetic fields. Here we report a theoretical description of ISRS where we do not make any semi-classical approximation and we treat both photonic and phononic degrees of freedom at the quantum level. The results of the quantum model are compared with semiclassical results and validated by means of spectrally resolved pump&probe measurements on α-quartz.

Excitation of coherent optical phonons in iron garnet by femtosecond laser pulses

We employed femtosecond pump-probe technique to investigate the dynamics of coherent optical phonons in iron garnet. A phenomenological symmetry-based consideration reveals that oscillations of the terahertz T2g mode are excited. Selective excitation by a linearly polarized pump and detection by a circularly polarized probe confirm that impulsive stimulated Raman scattering (ISRS) is the driving force for the coherent phonons. Experimental results obtained from ISRS measurements reveal excellent agreement with spontaneous Raman spectroscopy data, analyzed by considering the symmetry of the phonon modes and corresponding excitation and detection selection rules.

Excitation of multiple phonon modes in copper metaborate CuB2O4 via nonresonant impulsive stimulated Raman scattering

Excitation of four coherent phonon modes of different symmetries has been realized in copper metaborate CuB$_2$O$_4$ via impulsive stimulated Raman scattering (ISRS). Phonons were detected by monitoring changes in the linear optical birefringence using the balanced-detection (BD) technique. We compare the results of BD-ISRS experiment to the polarized spontaneous Raman scattering spectra. We show that the agreement between the two sets of data obtained by these allied techniques in a wide phonon frequencies range of 4-14 THz can be achieved by rigorously taking into account the symmetry of the phonon modes, and the corresponding excitation and detection selection rules. It is also important to account for the difference between incoherent and coherent phonons in terms of their contributions to the Raman scattering process. This comparative analysis highlights the importance of the ratio between the frequency of a particular mode, and the pump and probe spectral widths. We demonstrate analytically that the pump and probe pulse durations of 90 and 50 fs, respectively, used in our experiments, limit the highest frequency of the excited and detected coherent phonon modes to 12 THz, and define their relative amplitudes.

Oxygen-dependent laser inactivation of murine norovirus using visible light lasers

BackgroundPrevious work indicated that an ultrashort pulse (USP) 425 nm laser is capable of inactivating murine norovirus (MNV: Virol. J. 11:20), perhaps via an impulsive stimulated Raman scattering (ISRS) mechanism, and does not substantially damage human plasma proteins (PLOS One 9:11). Here, further investigation of virus inactivation by laser light is performed.MethodsIn this study, we evaluate whether inactivation of MNV is specific to the USP wavelength of 425 nm, or if it occurs at other visible wavelengths, using a tunable mode-locked Ti-Sapphire laser that has been frequency doubled to generate femtosecond pulses at wavelengths of 400, 408, 425, 450, 465, and 510 nm. Continuous Wave (CW) lasers are also applied. Singlet oxygen enhancers are used to evaluate the sensitivity of MNV to singlet oxygen and oxygen quenchers are used to evaluate effects on virus inactivation as compared to untreated controls.Results> 3 log10 inactivation of MNV pfu occurs after irradiation with an average power of 150 mW at wavelengths of 408, 425 or 450 nm femtosecond-pulsed light for 3 h. Thus results suggest that the mechanism by which a laser inactivates the virus is not wavelength-specific. Furthermore, we also show that irradiation using a continuous wave (CW) laser of similar power at 408 nm also yields substantial MNV inactivation indicating that inactivation does not require a USP. Use of photosensitizers, riboflavin, rose bengal and methylene blue that generate singlet oxygen substantially improves the efficiency of the inactivation. The results indicate a photochemical mechanism of the laser-induced inactivation where the action of relatively low power blue laser light generates singlet oxygen.ConclusionResults suggest formation of short-lived reactive oxygen species such as singlet oxygen by visible laser light as the cause of virus inactivation rather than via an ISRS mechanism which induces resonant vibrations.

Experimental determination of the interatomic potential in LiNbO3 via ultrafast lattice control

We present a direct comparison between resonant terahertz (THz) and nonresonant impulsive stimulated Raman scattering (ISRS) excitation of phonon-polaritons in ferroelectric lithium niobate. THz excitation offers advantages of selectively driving only the forward propagating phonon-polariton mode to exceedingly high amplitudes, without complications due to nonlinear processes at the high 800 nm pump fluences used in Raman excitation. At peak-to-peak THz electric field strengths exceeding 1 MV/cm, the ferroelectric lattice is driven into the anharmonic regime, allowing experimental determination of the shape of the potential energy surface along this vibrational coordinate.

Impulsive SRS in tetragonal t-YVO4, t-GdVO4and monoclinic m-LaVO4vanadate host-crystals for Ln3+-lasant ions

Tetragonal t-YVO4, t-GdVO4 and monoclinic m-LaVO4 are widely known as host-matrix materials for Ln3+-lasant ions in high-gain SRS-active crystals. In this study, many phonon impulsive stimulated Raman scattering (ISRS) was excited under femtosecond pumping for these materials. All of the observed χ(3)-non-linear lasing components were attributed to the vibrations of the [VO4]3− structural units of these vanadates. The article gives a short review (in table form) of all known SRS-active crystals with tetragonal zircon-type (ZrSiO4) and monazite-type (CePO4) structure and their observed χ(3)-nonlinear optical effects.

Influence of pulse width and detuning on coherent phonon generation

We investigated the coherent phonon generation mechanism by irradiation of an ultrashort pulse with a simple two-level model. Our derived formulation shows that both impulsive stimulated Raman scattering (ISRS) and impulsive absorption (IA) simultaneously occur, and phonon wave packets are generated in the electronic ground and excited states by ISRS and IA, respectively. We identify the dominant process from the amplitude of the phonon oscillation. For short pulse widths, ISRS is very small and becomes larger as the pulse width increases. We also show that the initial phase is dependent on the pulse width and the detuning.

Studies of inactivation mechanism of non-enveloped icosahedral virus by a visible ultrashort pulsed laser

BackgroundLow-power ultrashort pulsed (USP) lasers operating at wavelengths of 425 nm and near infrared region have been shown to effectively inactivate viruses such as human immunodeficiency virus (HIV), M13 bacteriophage, and murine cytomegalovirus (MCMV). It was shown previously that non-enveloped, helical viruses such as M13 bacteriophage, were inactivated by a USP laser through an impulsive stimulated Raman scattering (ISRS) process. Recently, enveloped virus like MCMV has been shown to be inactivated by a USP laser via protein aggregation induced by an ISRS process. However, the inactivation mechanism for a clinically important class of viruses – non-enveloped, icosahedral viruses remains unknown.Results and discussionsWe have ruled out the following four possible inactivation mechanisms for non-enveloped, icosahedral viruses, namely, (1) inactivation due to ultraviolet C (UVC) photons produced by non-linear optical process of the intense, fundamental laser beam at 425 nm; (2) inactivation caused by thermal heating generated by the direct laser absorption/heating of the virion; (3) inactivation resulting from a one-photon absorption process via chromophores such as porphyrin molecules, or indicator dyes, potentially producing reactive oxygen or other species; (4) inactivation by the USP lasers in which the extremely intense laser pulse produces shock wave-like vibrations upon impact with the viral particle. We present data which support that the inactivation mechanism for non-enveloped, icosahedral viruses is the impulsive stimulated Raman scattering process. Real-time PCR experiments show that, within the amplicon size of 273 bp tested, there is no damage on the genome of MNV-1 caused by the USP laser irradiation.ConclusionWe conclude that our model non-enveloped virus, MNV-1, is inactivated by the ISRS process. These studies provide fundamental knowledge on photon-virus interactions on femtosecond time scales. From the analysis of the transmission electron microscope (TEM) images of viral particles before and after USP laser irradiation, the locations of weak structural links on the capsid of MNV-1 were revealed. This important information will greatly aid our understanding of the structure of non-enveloped, icosahedral viruses. We envision that this non-invasive, efficient viral eradication method will find applications in the disinfection of pharmaceuticals, biologicals and blood products in the near future.

The effect of n- and p-type doping on coherent phonons in GaN

The effect of doping on the carrier–phonon interaction in wurtzite GaN is investigated by pump–probe reflectivity measurements using 3.1 eV light in near resonance with the fundamental band gap of 3.39 eV. Coherent modulations of the reflectivity due to the E2 and A1(LO) modes, as well as the 2A1(LO) overtone are observed. Doping of acceptor and donor atoms enhances the dephasing of the polar A1(LO) phonon via coupling with plasmons, with the effect of donors being stronger. Doping also enhances the relative amplitude of the coherent A1(LO) phonon with respect to that of the high-frequency E2 phonon, though it does not affect the relative intensity in Raman spectroscopic measurements. We attribute this enhanced coherent amplitude to the transient depletion field screening (TDFS) excitation mechanism, which, in addition to impulsive stimulated Raman scattering (ISRS), contributes to the generation of coherent polar phonons even for sub-band gap excitation. Because the TDFS mechanism requires photoexcitation of carriers, we argue that the interband transition is made possible at a surface with photon energies below the bulk band gap through the Franz–Keldysh effect.

Selection rules for angular momentum transfer via impulsive stimulated Raman scattering

Impulsive stimulated Raman scattering (ISRS) plays a key role in coherent control of low-energy rotational resonances. Femtosecond laser pulses are widely employed to utilize ISRS because they are broadband and can cover the needed frequencies in a single pulse. Here, we show theoretically that the ISRS process is expressed as a linear response to the instantaneous Stokes parameters (ISPs) of the laser pulse. These IPSs expressed in rotational coordinates are then shown to be responsible for the angular momentum transfer from light to matter. These relationships have led to the designs of spectral profiles and polarization states of light pulses that should selectively excite particular rotational modes.

Femtosecond pulse excitation of vibrational wave packets in chloroform: The effect of gold nanoparticles

Excitation of pure chloroform or a gold colloid in chloroform (average nanoparticle diameter of 2.5 nm) with 740-nm femtosecond pulses of 23-fs duration leads to oscillations in the differential absorption signal ΔA(λ, t) recorded using white-light continuum. The main oscillation modes for both systems are close to the chloroform Raman resonance frequencies of 260, 367, and 668 cm−1. However, marked narrowing and splitting of bands in the Fourier-transform spectra of oscillations are observed in the system of gold colloid in chloroform. The intensity of oscillations linearly increases with the pump pulse intensity in the cases of pure chloroform and the system of gold colloid in chloroform. Apparently, the principal mechanism of excitation of coherent packets in chloroform is femtosecond impulsive stimulated Raman scattering (ISRS). Dissolution of gold nanoparticles leads to a four- to sixfold enhancement of the Raman resonance signal of chloroform in the gold colloid as compared with pure chloroform. The increase in the intensity of Raman resonances is presumably due to amplification in the near field of gold nanoparticles.

Influence of two photon absorption induced free carriers on coherent polariton and phonon generation in ZnTe crystals

Combination of femtosecond Kerr, two photon absorption, and impulsive stimulated Raman scattering (ISRS) experiments have been carried out to investigate the effect of pulse energy and crystal temperature on the generation of coherent polaritons and phonons in ⟨110⟩ cut ZnTe single crystals of three different resistivities. We demonstrate that the effect of two photon induced free carriers on the creation of both the polaritons and phonons is largest at 4 K where the free carrier lifetime is enhanced. The temperature dependant ISRS on high and low purity ZnTe crystals allows us to unambiguously assign the phonon mode at 3.5 THz to the longitudinal acoustic mode at X-point in the Brillouin zone, LA(X).