Following the Nonthermal Phase Transition in Niobium Dioxide by Time-Resolved Harmonic Spectroscopy.

Photoinduced phase transitions in correlated materials promise diverse applications from ultrafast switches to optoelectronics. Resolving those transitions and possible metastable phases temporally are key enablers for these applications, but challenge existing experimental approaches. Extreme nonlinear optics can help probe phase changes, as higher-order nonlinearities have higher sensitivity and temporal resolution to band structure and lattice deformations. Here the ultrafast transition from the semiconducting to the metallic phases in polycrystalline thin-film NbO_{2} is investigated by time-resolved harmonic spectroscopy. The emission strength of all harmonic orders shows a steplike suppression when the excitation fluence exceeds a threshold (∼11-12 mJ/cm^{2}), below the fluence required for the thermal transition-a signature of the nonthermal emergence of a metallic phase within 100±20 fs. This observation is backed by full ab initio simulations as well as a 1D chain model of high-harmonic generation from both phases. Our results demonstrate femtosecond harmonic probing of phase transitions and nonthermal dynamics in solids.

Polaritonic molecular clock for all-optical ultrafast imaging of wavepacket dynamics without probe pulses.

Conventional approaches to probing ultrafast molecular dynamics rely on the use of synchronized laser pulses with a well-defined time delay. Typically, a pump pulse excites a molecular wavepacket. A subsequent probe pulse can then dissociate or ionize the molecule, and measurement of the molecular fragments provides information about where the wavepacket was for each time delay. Here, we propose to exploit the ultrafast nuclear-position-dependent emission obtained due to large light-matter coupling in plasmonic nanocavities to image wavepacket dynamics using only a single pump pulse. We show that the time-resolved emission from the cavity provides information about when the wavepacket passes a given region in nuclear configuration space. This approach can image both cavity-modified dynamics on polaritonic (hybrid light-matter) potentials in the strong light-matter coupling regime and bare-molecule dynamics in the intermediate coupling regime of large Purcell enhancements, and provides a route towards ultrafast molecular spectroscopy with plasmonic nanocavities.

Cumulant expansion for the treatment of light-matter interactions in arbitrary material structures.

Strong coupling of quantum emitters with confined electromagnetic modes of nanophotonic structures may be used to change optical, chemical, and transport properties of materials, with significant theoretical effort invested toward a better understanding of this phenomenon. However, a full theoretical description of both matter and light is an extremely challenging task. Typical theoretical approaches simplify the description of the photonic environment by describing it as a single mode or few modes. While this approximation is accurate in some cases, it breaks down strongly in complex environments, such as within plasmonic nanocavities, and the electromagnetic environment must be fully taken into account. This requires the quantum description of a continuum of bosonic modes, a problem that is computationally hard. We here investigate a compromise where the quantum character of light is taken into account at modest computational cost. To do so, we focus on a quantum emitter that interacts with an arbitrary photonic spectral density and employ the cumulant, or cluster, expansion method to the Heisenberg equations of motion up to first, second, and third order. We benchmark the method by comparing it with exact solutions for specific situations and show that it can accurately represent dynamics for many parameter ranges.

Even harmonic generation in isotropic media of dissociating homonuclear molecules.

Isotropic gases irradiated by long pulses of intense IR light can generate very high harmonics of the incident field. It is generally accepted that, due to the symmetry of the generating medium, be it an atomic or an isotropic molecular gas, only odd harmonics of the driving field can be produced. Here we show how the interplay of electronic and nuclear dynamics can lead to a marked breakdown of this standard picture: a substantial part of the harmonic spectrum can consist of even rather than odd harmonics. We demonstrate the effect using ab-initio solutions of the time-dependent Schrödinger equation for and its isotopes in full dimensionality. By means of a simple analytical model, we identify its physical origin, which is the appearance of a permanent dipole moment in dissociating homonuclear molecules, caused by light-induced localization of the electric charge during dissociation. The effect arises for sufficiently long laser pulses and the region of the spectrum where even harmonics are produced is controlled by pulse duration. Our results (i) show how the interplay of femtosecond nuclear and attosecond electronic dynamics, which affects the charge flow inside the dissociating molecule, is reflected in the nonlinear response, and (ii) force one to augment standard selection rules found in nonlinear optics textbooks by considering light-induced modifications of the medium during the generation process.

Enhancing High-Order Harmonic Generation in Light Molecules by Using Chirped Pulses.

One of the current challenges in high-harmonic generation is to extend the harmonic cutoff to increasingly high energies while maintaining or even increasing the efficiency of the high-harmonic emission. Here we show that the combined effect of down-chirped pulses and nuclear dynamics in light molecules allows one to achieve this goal, provided that long enough IR pulses are used to allow the nuclei to move well outside the Franck-Condon region. We also show that, by varying the duration of the chirped pulse or by performing isotopic substitution while keeping the pulse duration constant, one can control the extension of the harmonic plateau.

Correlated electron and nuclear dynamics in strong field photoionization of H(2)(+).

We present a theoretical study of H(2)(+) ionization under strong IR femtosecond pulses by using a method designed to extract correlated (2D) photoelectron and proton kinetic energy spectra. The results show two distinct ionization mechanisms-tunnel and multiphoton ionization-in which electrons and nuclei do not share the energy from the field in the same way. Electrons produced in multiphoton ionization share part of their energy with the nuclei, an effect that shows up in the 2D spectra in the form of energy-conservation fringes similar to those observed in weak-field ionization of diatomic molecules. In contrast, tunneling electrons lead to fringes whose position does not depend on the proton kinetic energy. At high intensity, the two processes coexist and the 2D plots show a very rich behavior, suggesting that the correlation between electron and nuclear dynamics in strong field ionization is more complex than one would have anticipated.

Pump-probe scheme to study the autoionization decay of optically-forbidden H2 doubly excited states.

A pump-probe scheme is proposed to investigate the autoionization dynamics of the optically forbidden Q(1)(1)Σ(g)(+) doubly excited states of the H(2) molecule. The scheme consists of a pump that contains an attosecond pulse train (APT) and an infrared (IR) pulse, which is phase-locked with the APT, and an IR probe identical to the former IR pulse. The dynamical information is obtained by analyzing the electron kinetic energy spectra (EKE) and proton kinetic energy spectra (PKE) as a function of the time delay between the pump and the probe. The essential requirement for an efficient population of the Q(1)(1)Σ(g)(+) states is that they are resonantly coupled to both the dipole-allowed Q(1)(1)Σ(u)(+) doubly excited states and the ground state of H(2) by the combined effect of the APT + IR fields.