Impulsive Vibrational Spectroscopy Research Articles

Mechanism of Hot-Carrier Photoluminescence in Sn-Based Perovskites.

Metal halide perovskites have shown exceptionally slow hot-carrier cooling, which has been attributed to various physical mechanisms without reaching a consensus. Here, experiment and theory are combined to unveil the carrier cooling process in formamidinium (FA) and caesium (Cs) tin triiodide thin films. Through impulsive vibrational spectroscopy and molecular dynamics, much shorter phonon dephasing times of the hybrid perovskite, which accounts for the larger blueshift in the photoluminescence seen at high excitation density for FASnI3 compared to CsSnI3 is reported. Density functional theory investigations reveal that the largest contribution to the blueshift is accounted by a giant, dynamic band-filling effect in Sn-based perovskites, which in turn can explain the cooling disparity with the Pb-based counterparts. Several years after the first experimental observations, here a deeper understanding of the cooling mechanism of these materials is provided. Design principles for hot-carrier materials, which may be useful for future implementations of hot-carrier solar cells are further provided.

Decoupling excitons from high-frequency vibrations in organic molecules

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon–carbon stretch modes (1,000–1,600 cm−1) has been thought to be unavoidable1,2. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton–vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680–800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm−1, frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

Simultaneous capturing phonon and electron dynamics in MXenes

Plasmonic MXenes are of particular interest, because of their unique electron and phonon structures and multiple surface plasmon effects, which are different from traditional plasmonic materials. However, to date, how electronic energy damp to lattice vibrations (phonons) in MXenes has not been unraveled. Here, we employed ultrafast broadband impulsive vibrational spectroscopy to identify the energy damping channels in MXenes (Ti3C2Tx and Mo2CTx). Distinctive from the well-known damping pathways, our results demonstrate a different energy damping channel, in which the Ti3C2Tx plasmonic electron energy transfers to coherent phonons by nonthermal electron mediation after Landau damping, without involving electron-electron scattering. Moreover, electrons are observed to strongly couple with A1g mode (~60 fs, 85–100%) and weakly couple with Eg mode (1–2 ps, 0–15%). Our results provide new insight into the electron-phonon interaction in MXenes, which allows the design of materials enabling efficient manipulation of electron transport and energy conversion.

Ultrafast impulsive Raman spectroscopy across the terahertz–fingerprint region

Broadband Raman spectroscopy (detection bandwidth >1000 cm − 1) is a valuable and widely used tool for understanding samples via label-free measurements of their molecular vibrations. Two important Raman spectral regions are the chemically specific “fingerprint” (200 to 1800 cm − 1) and “low-frequency” or “terahertz” (THz) (<200 cm − 1; <6 THz) regions, which mostly contain intramolecular and intermolecular vibrations, respectively. These two regions are highly complementary; broadband simultaneous measurement of both regions can provide a big picture comprising information about molecular structures and interactions. Although techniques for acquiring broadband Raman spectra covering both regions have been demonstrated, these methods tend to have spectral acquisition rates <10 spectra / s, prohibiting high-speed applications, such as Raman imaging or vibrational detection of transient phenomena. Here, we demonstrate a single-laser method for ultrafast (24,000 spectra / s) broadband Raman spectroscopy covering both THz and fingerprint regions. This is achieved by simultaneous detection of Sagnac-enhanced impulsive stimulated Raman scattering (SE-ISRS; THz-sensitive) and Fourier-transform coherent anti-Stokes Raman scattering (FT-CARS; fingerprint-sensitive). With dual-detection impulsive vibrational spectroscopy, the SE-ISRS signal shows a >500 × enhancement of <6.5 THz sensitivity compared with that of FT-CARS, and the FT-CARS signal shows a >10 × enhancement of fingerprint sensitivity above 1000 cm − 1 compared with that of SE-ISRS.

Zone-Folded Longitudinal Acoustic Phonons Driving Self-Trapped State Emission in Colloidal CdSe Nanoplatelet Superlattices

Colloidal CdSe nanoplatelets (NPLs) have substantial potential in light-emitting applications because of their quantum-well-like characteristics. The self-trapped state (STS), originating from strong electron-phonon coupling (EPC), is promising in white light luminance because of its broadband emission. However, achieving STS in CdSe NPLs is extremely challenging because of their intrinsic weak EPC nature. Herein, we developed a strong STS emission in the spectral range of 450-600 nm by building superlattice (SL) structures with colloidal CdSe NPLs. We demonstrated that STS is generated via strong coupling of excitons and zone-folded longitudinal acoustic phonons with formation time of ∼450 fs and localization length of ∼0.56 nm. The Huang-Rhys factor, describing the EPC strength in SL structure, is estimated to be ∼19.9, which is much larger than that (∼0.1) of monodispersed CdSe NPLs. Our results provide an in-depth understanding of STS and a platform for generating and manipulating STS by designing SL structures.

Simulation of Impulsive Vibrational Spectroscopy.

In the present work we applied a fully atomistic electron-nuclear real-time propagation protocol to compute the impulsive vibrational spectroscopy of the five DNA/RNA nucleobases in order to study the very first steps (subpicosecond) of their energy distribution after UV excitation. We observed that after the pump pulse absorption the system is prepared in a coherent superposition of the ground and the pumped electronic excited states in the equilibrium geometry of the ground state. Furthermore, for relatively low fluency values of the pump pulse, the dominant contribution to the electronic wave function of the coherent state is of the ground state and the mean potential energy surface within the Ehrenfest approximation is similar to that of the ground state. As a consequence, the molecular displacements are better correlated with ground-state normal modes. On the other hand, when the pump fluency is increased the excited-state contribution to the electronic wave function becomes more important and the mean potential energy surface resembles more that of the excited state, producing a better correlation between the molecular displacements and the excited-state normal modes. Finally, it has been observed that the impulsive activation of several vibrational modes upon electronic excitation is triggered by the development of excited-state forces which accelerate the nuclei from their equilibrium positions causing a distribution of the absorbed electronic energy on the nuclear degrees of freedom and could be closely related to the driving force of the ultrafast nonradiative deactivation observed in these systems.

Mapping the ultrafast vibrational dynamics of all-trans and 13-Cis retinal isomerization in Anabaena Sensory Rhodopsin

The ground and excited state evolution of fingerprint vibrational modes of all-trans-and 13-cis-retinal are mapped by impulsive vibrational spectroscopy. All-trans-retinal shows slower frequency shift dynamics in the excited state in comparison to 13-cis-retinal.

Probing femtosecond lattice displacement upon photo-carrier generation in lead halide perovskite

Electronic properties and lattice vibrations are expected to be strongly correlated in metal-halide perovskites, due to the soft fluctuating nature of their crystal lattice. Thus, unveiling electron–phonon coupling dynamics upon ultrafast photoexcitation is necessary for understanding the optoelectronic behavior of the semiconductor. Here, we use impulsive vibrational spectroscopy to reveal vibrational modes of methylammonium lead-bromide perovskite under electronically resonant and non-resonant conditions. We identify two excited state coherent phonons at 89 and 106 cm−1, whose phases reveal a shift of the potential energy minimum upon ultrafast photocarrier generation. This indicates the transition to a new geometry, reached after approximately 90 fs, and fully equilibrated within the phonons lifetime of about 1 ps. Our results unambiguously prove that these modes drive the crystalline distortion occurring upon photo-excitation, demonstrating the presence of polaronic effects.

Surface-Enhanced Impulsive Coherent Vibrational Spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) has attracted a lot of attention in molecular sensing because of the remarkable ability of plasmonic metal nanostructures to enhance the weak Raman scattering process. On the other hand, coherent vibrational spectroscopy triggered by impulsive excitation using ultrafast laser pulses provides complete information about the temporal evolution of molecular vibrations, allowing dynamical processes in molecular systems to be followed in “real time”. Here, we combine these two concepts and demonstrate surface-enhanced impulsive vibrational spectroscopy. The vibrational modes of the ground and excited states of poly[2-methoxy-5-(2-ethylhexyloxy)−1,4-phenylenevinylene] (MEH-PPV), spin-coated on a substrate covered with monodisperse silver nanoparticles, are impulsively excited with a sub-10 fs pump pulse and characterized with a delayed broad-band probe pulse. The maximum enhancement in the spectrally and temporally resolved vibrational signatures averaged over the whole sample is about 4.6, while the real-time information about the instantaneous vibrational amplitude together with the initial vibrational phase is preserved. The phase is essential to determine the vibrational contributions from the ground and excited states.

Principles and Applications of Broadband Impulsive Vibrational Spectroscopy.

We present an experimental setup for recording vibrational coherences and thereby Raman spectra of molecules in their ground and excited electronic states over the 50-3000 cm(-1) spectral range using broadband impulsive vibrational spectroscopy. Our approach relies on the combination of a <10 fs excitation pulse with an uncompressed white light continuum probe, which drastically reduces experimental complexity compared to frequency domain based techniques. We discuss the parameters determining vibrational coherence amplitudes, outline how to optimize the experimental setup including approaches aimed at conclusively assigning vibrational coherences to specific electronic states, and provide a clear comparison with existing techniques. To demonstrate the applicability of our spectroscopic approach we conclude with several examples revealing the evolution of vibrational coherence in rhodopsin and β-carotene.

Population-controlled impulsive vibrational spectroscopy: background- and baseline-free Raman spectroscopy of excited electronic states.

We have developed the technique of population-controlled impulsive vibrational spectroscopy (PC-IVS) aimed at providing high-quality, background-free Raman spectra of excited electronic states and their dynamics. Our approach consists of a modified transient absorption experiment using an ultrashort (<10 fs) pump pulse with additional electronic excitation and control pulses. The latter allows for the experimental isolation of excited-state vibrational coherence and, hence, vibrational spectra. We illustrate the capabilities of PC-IVS by reporting the Raman spectra of well-established molecular systems such as the carotenoid astaxanthin and trans-stilbene and present the first excited-state Raman spectra of the retinal protonated Schiff base chromophore in solution. Our approach, illustrated here with impulsive vibrational spectroscopy, is equally applicable to transient and even multidimensional infrared and electronic spectroscopies to experimentally isolate spectroscopic signatures of interest.

Broad-Band Impulsive Vibrational Spectroscopy of Excited Electronic States in the Time Domain.

We demonstrate that transient absorption spectroscopy performed with an ultrashort pump pulse and a chirped, broad-band probe pulse is capable of recording full vibrational spectra of excited electronic states in the time domain. The resulting spectra do not suffer from the nontrivial baselines and line shapes often encountered in frequency domain techniques and enable optimal and automated subtraction of background signatures. Probing the molecular dynamics continuously over a broad energy bandwidth makes it possible to confidently assign the vibrational coherences to specific electronic states and suggests the existence of mode-specific absorption spectra reminiscent of resonance Raman intensity analysis. The first observation of the nominally forbidden one-photon ground to first excited electronic state transition in β-carotene demonstrates the high sensitivity of our approach. Our results provide a first glimpse of the immense potential of broad-band impulsive vibrational spectroscopy (BB-IVS) to study ultrafast chemical reaction dynamics.

Following Photoinduced Dynamics in Bacteriorhodopsin with 7-fs Impulsive Vibrational Spectroscopy

Sub-10-fs laser pulses are used to impulsively photoexcite bacteriorhodopsin (BR) suspensions and probe the evolution of the resulting vibrational wave packets. Fourier analysis of the spectral modulations induced by transform-limited as well as linearly chirped excitation pulses allows the delineation of excited- and ground-state contributions to the data. On the basis of amplitude and phase variations of the modulations as a function of the dispersed probe wavelength, periodic modulations in absorption above 540 nm are assigned to ground-state vibrational coherences induced by resonance impulsive Raman spectral activity (RISRS). Probing at wavelengths below 540 nm-the red edge of the intense excited-state absorption band-uncovers new vibrational features which are accordingly assigned to wave packet motions along bound coordinates on the short-lived reactive electronic surface. They consist of high- and low-frequency shoulders adjacent to the strong C=C stretching and methyl rock modes, respectively, which have ground-state frequencies of 1008 and 1530 cm-1. Brief activity centered at approximately 900 cm-1, which is characteristic of ground-state HOOP modes, and strong modulations in the torsional frequency range appear as well. Possible assignments of the bands and their implication to photoinduced reaction dynamics in BR are discussed. Reasons for the absence of similar signatures in the pump-probe spectral modulations at longer probing wavelengths are considered as well.