Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g-factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science.

Ultrafast 2D spectroscopy uses correlated multiple light−matter interactions for retrieving dynamic features that may otherwise be hidden under the linear spectrum; its extension to the terahertz regime of the electromagnetic spectrum, where a rich variety of material degrees of freedom reside, remains an experimental challenge. We report a demonstration of ultrafast 2D terahertz spectroscopy of gas-phase molecular rotors at room temperature. Using time-delayed terahertz pulse pairs, we observe photon echoes and other nonlinear signals resulting from molecular dipole orientation induced by multiple terahertz field−dipole interactions. The nonlinear time domain orientation signals are mapped into the frequency domain in 2D rotational spectra that reveal J-state-resolved nonlinear rotational dynamics. The approach enables direct observation of correlated rotational transitions and may reveal rotational coupling and relaxation pathways in the ground electronic and vibrational state.

Spectral features in two-dimensional Fourier transform optical spectroscopy were selectively enhanced using pulse shapes and sequences designed to amplify specific excited-state resonances. The enhancement was achieved by tailoring a small set of input parameters that control the amplitude and phase profiles of the excitation fields, coherently driving or suppressing selected resonances. The tailored pulse shapes were applied to enhance exciton and biexciton coherences in a semiconductor quantum well. Enhancement of selected resonances was demonstrated even in cases of spectrally overlapping features and complex many-body interactions. Modifications in the 2D spectral line shapes due to the tailored waveforms were calculated using the optical Bloch equations.

We present two-dimensional Fourier transform optical spectroscopy measurements of two types of molecular J-aggregate thin films and show that temperature-dependent dynamical effects govern exciton delocalization at all temperatures, even in the presence of significant inhomogeneity. Our results indicate that in the tested molecular aggregates, even when the static structure disorder dominates exciton dephasing dynamics, the extent of exciton delocalization may be limited by dynamical fluctuations, mainly exciton–phonon coupling. Thus inhomogeneous dephasing may mediate the exciton coherence time whereas dynamical fluctuations mediate the exciton coherence length.

We report strong THz-induced transparency in CVD-grown graphene where 92–96% of the peak-field is transmitted compared to 74% at lower field strength. Time-resolved THz pump/THz probe studies reveal that the absorption recovers in 2–3 ps. The induced transparency is believed to arise from nonlinear pumping of carriers in graphene which suppresses the mobility and consequently the conductivity in a spectral region where the light–matter interaction is particularly strong.

The Coulomb correlations between photoexcited charged particles in materials such as photosynthetic complexes, conjugated polymer systems, J-aggregates, and bulk or nanostructured semiconductors produce a hierarchy of collective electronic excitations, for example, excitons, and biexcitons, which may be harnessed for applications in quantum optics, light-harvesting, or quantum information technologies. These excitations represent correlations among successively greater numbers of electrons and holes, and their associated multiple-quantum coherences could reveal detailed information about complex many-body interactions and dynamics. However, unlike single-quantum coherences involving excitons, multiple-quantum coherences do not radiate; consequently, they have largely eluded direct observation and characterization. In this Account, we present a novel optical technique, two-quantum, two-dimensional Fourier transform optical spectroscopy (2Q 2D FTOPT), which allows direct observation of the dynamics of multiple exciton states that reflect the correlations of their constituent electrons and holes. The approach is based on closely analogous methods in NMR, in which multiple phase-coherent fields are used to drive successive transitions such that multiple-quantum coherences can be accessed and probed. In 2Q 2D FTOPT, a spatiotemporal femtosecond pulse-shaping technique has been used to overcome the challenge of control over multiple, noncollinear, phase-coherent optical fields in experimental geometries used to isolate selected signal contributions through wavevector matching. We present results from a prototype GaAs quantum well system, which reveal distinct coherences of biexcitons that are formed from two identical excitons or from two excitons that have holes in different spin sublevels (“heavy-hole” and “light-hole” excitons). The biexciton binding energies and dephasing dynamics are determined, and changes in the dephasing rates as a function of the excitation density are observed, revealing still higher order correlations due to exciton−biexciton interactions. Two-quantum coherences due to four-particle correlations that do not involve bound biexciton states but that influence the exciton properties are also observed and characterized. The 2Q 2D FTOPT technique allows many-body interactions that cannot be treated with a mean-field approximation to be studied in detail; the pulse-shaping approach simplifies greatly what would have otherwise been daunting measurements. This spectroscopic tool might soon offer insight into specific applications, for example, in detailing the interactions that affect how electronic energy moves within the strata of organic photovoltaic cells.

Generation of near single-cycle THz pulses from lithium niobate with 3.3 μJ energy, 3.3 mW average power, 1.2 THz central frequency and 4 MW peak power was demonstrated by tilting the intensity front of the pump pulses from a 1 kHz Ti:sapphire laser. THz pulse intensity as high as 200 MW/cm2 was achieved. The energy conversion efficiency was 7 × 10−4. The capability of the present scheme to generate high energy shaped THz pulses was also demonstrated by using a sequence of optical pump pulses.

Abstract

Because multiple laser shots are typically required to monitor ultrafast photochemical reaction dynamics, sample depletion and product accumulation have greatly restricted the range of substrates and structural environments amenable to study. By implementing a two-dimensional spatial delay gradient across the profile of a femtosecond probe pulse, we can monitor in a single laser shot organic crystalline reaction dynamics despite the formation of permanent photoproducts that cannot be conveniently removed. We monitored the photolysis of the triiodide anion, I₃⁻, and subsequent recombination or relaxation of its reaction products, in three very different pure organic molecular crystals. The experimental results and associated molecular dynamics simulations illustrate the intimate connection between lattice structure and reaction dynamics, highlighting the role of lattice constraints in directing phase-coherent geminate recombination of photofragments within a crystalline reaction cage.

A novel single-shot femtosecond spectroscopy technique permits real-time examination of irreversible decomposition in energetic solids. In a single laser shot, measurements at 400 different temporal delays are recorded to cover a total temporal range of more than 10 ps in 30 fs steps. This is accomplished by using two crossed echelon optics to separate a single probe pulse into 400 spatially and temporally separate probe pulses. Dielectric breakdown of silica glass and of 1,3,3-trinitroazetidine (TNAZ) was observed to occur on the time scale of the 50-fs pump pulse duration.