Using real-space view of high harmonic generation (HHG) in solids, we develop a physically transparent and gauge-invariant approach for distinguishing intraband and interband HHG mechanisms. Our approach relies on resolving the harmonic emission according to the separation between Wannier states involved in radiative transitions. We show that the intra- and inter-band HHG emission exhibit striking qualitative differences in their dependence on this separation and can be clearly distinguished using the Wannier basis.

Cumulant mapping has been recently suggested [Frasinski, Phys. Chem. Chem. Phys. 24, 207767 (2022)] as an efficient approach to observing multi-particle fragmentation pathways, while bypassing the restrictions of the usual coincidence-measurement approach. We present a formal analysis of the cumulant-mapping technique in the presence of moderate external noise, which induces spurious correlations between the fragments. Suppression of false-cumulant signal may impose severe restrictions on the stability of the experimental setup and/or the permissible average event rate, which increase with the cumulant order. We demonstrate that cumulant mapping in an imperfect apparatus remains competitive for dominant processes and for pathways with a background-free marker fragment. We further show that the false-cumulant contributions increase faster than linearly with the average event rate, providing a simple test for the experimental data analysis.

High-resolution coherent Raman spectroscopic measurements of all three tritium-containing molecular hydrogen isotopologues T$_2$, DT and HT were performed to determine the ground electronic state fundamental Q-branch ($v=0 \rightarrow 1, \Delta J = 0$) transition frequencies at accuracies of$0.0005$ cm$^{-1}$. An over hundred-fold improvement in accuracy over previous experiments allows the comparison with the latest ab initio calculations in the framework of Non-Adiabatic Perturbation Theory including nonrelativisitic, relativisitic and QED contributions. Excellent agreement is found between experiment and theory, thus providing a verification of the validity of the NAPT-framework for these tritiated species. While the transition frequencies were corrected for ac-Stark shifts, the contributions of non-resonant background as well as quantum interference effects between resonant features in the nonlinear spectroscopy were quantitatively investigated, also leading to corrections to the transition frequencies. Methods of saturated CARS with the observation of Lamb dips, as well as the use of continuous-wave radiation for the Stokes frequency were explored, that might pave the way for future higher-accuracy CARS measurements.

Brunel radiation appears as a result of a two-step process of photo-ionization and subsequent acceleration of electron, without the need of electron recollision. We show that for generation of Brunel harmonics at all frequencies the subcycle ionization dynamics is of critical importance. Namely, such harmonics disappear at low pump intensities when the ionization dynamics depends only on the slow envelope (so called multiphoton ionization regime) and not on the instantaneous field. Nevertheless, if the pump pulse contains incommensurate frequencies, Brunel mechanism does generate new frequencies even in the multiphoton ionization regime.

Biomolecules couple to their aqueous environment through a variety of noncovalent interactions. Local structures at the surface of DNA and RNA are frequently determined by hydrogen bonds with water molecules, complemented by non-specific electrostatic and many-body interactions. Structural fluctuations of the water shell result in fluctuating Coulomb forces on polar and/or ionic groups of the biomolecular structure and in a breaking and reformation of hydrogen bonds. Two-dimensional infrared (2D-IR) spectroscopy of vibrational modes of DNA and RNA gives insight into local hydration geometries, elementary molecular dynamics, and the mechanisms behind them. In this chapter, recent results from 2D-IR spectroscopy of native and artificial DNA and RNA are presented, together with theoretical calculations of molecular couplings and molecular dynamics simulations. Backbone vibrations of DNA and RNA are established as sensitive noninvasive probes of the complex behavior of hydrated helices. The results reveal the femtosecond fluctuation dynamics of the water shell, the short-range character of Coulomb interactions, and the strength and fluctuation amplitudes of interfacial electric fields.

Information processing currently reaches speeds as high as 800 GHz. However, the underlying transistor technology is quickly approaching its fundamental limits and further progress requires a disruptive approach. One such path is to manipulate quantum properties of solids, such as the valley degree of freedom, with ultrashort controlled lightwaves. Here we employ a sequence of few-optical-cycle visible pulses controlled with attosecond precision to excite and switch the valley pseudospin in a 2D semiconductor. We show that a pair of pulses separated in time with linear orthogonal polarizations can induce a valley-selective population. Additionally, exploiting a four-pump excitation protocol, we perform logic operations such as valley de-excitation and re-excitation at room temperature at rates as high as ~10 THz.

We describe a unified numerical model which allows fast and accurate simulation of nonlinear light propagation in nanoparticle composites, including various effects such as group velocity dispersion, second- and third-order nonlinearity, quasi-free-carrier formation and plasma contribution, exciton dynamics, scattering and so on. The developed software package SOLPIC is made available for the community. Using this model, we analyze and optimize efficient generation of THz radiation by two-color pulses in ZnO/fused silica composite, predicting an efficiency of 3\%. We compare the role of various nonlinear effects contributing to the frequency conversion, and show that optimum conditions of THz generation differ from those expected intuitively.

We propose a new concept for generation of ultrashort pulses based on transient plasmonic resonance in nanoparticle composites. Photoionization and free-carriers plasma change the susceptibility of nanoparticles on a few-femtosecond scale. This results in a narrow time window during the pump pulse duration when the system is in plasmonic resonance, accompanied by a short burst of the local field. During this process, frequency-tunable few-fs pulses are generated. We elucidate the details of the above mechanism, and investigate the influences of different contributing processes.

UKRmol-scripts is a set of Perl scripts to automatically run the UKRmol+ codes, a complex software suite based on the R-matrix method to calculate fixed-nuclei photoionization and electron- and positron-scattering for polyatomic molecules. Starting with several basic parameters, the scripts operatively produce all necessary input files and run all codes for electronic structure and scattering calculations as well as gather the more frequently required outputs. The scripts provide a simple way to run such calculations for many molecular geometries concurrently and collect the resulting data for easier post-processing and visualization. We describe the structure of the scripts and the input parameters as well as provide examples for photoionization and electron and positron collisions with molecules. The codes are freely available from Zenodo.

Solids exposed to intense electric fields release electrons through tunnelling. This fundamental quantum process lies at the heart of various applications, ranging from high brightness electron sources in DC operation to petahertz vacuum electronics in laser-driven operation. In the latter process, the electron wavepacket undergoes semiclassical dynamics in the strong oscillating laser field, similar to strong-field and attosecond physics in the gas phase. There, the sub-cycle electron dynamics has been determined with a stunning precision of tens of attoseconds, but at solids the quantum dynamics including the emission time window has so far not been measured. Here we show that two-colour modulation spectroscopy of backscattering electrons uncovers the sub-optical-cycle strong-field emission dynamics from nanostructures, with attosecond precision. In our experiment, photoelectron spectra of electrons emitted from a sharp metallic tip are measured as function of the relative phase between the two colours. Projecting the solution of the time-dependent Schr\"odinger equation onto classical trajectories relates phase-dependent signatures in the spectra to the emission dynamics and yield an emission duration of $710\pm30$ attoseconds by matching the quantum model to the experiment. Our results open the door to the quantitative timing and precise active control of strong-field photoemission in solid state and other systems and have direct ramifications for diverse fields such as ultrafast electron sources, quantum degeneracy studies and sub-Poissonian electron beams, nanoplasmonics and petahertz electronics.

Brunel harmonics appear in the optical response of an atom in process of laser-induced ionization, when the electron leaves the atom and is accelerated in the strong optical field. In contrast to recollision-based harmonics, the Brunel mechanism does not require the electron returning to the core. Here we show that in the presence of a strong ionizing terahertz (THz) field, even a weak driving field at the optical frequencies allow for generating Brunel harmonics effectively. The strong ionizing THz pump suppresses recollisions, making Brunel dominant in a wide spectral range. High-order Brunel harmonics may form a coherent carrier-envelope-phase insensitive supercontinuum, compressible into an isolated pulse with the duration down to 100 attoseconds.

Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps towards understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species amongst the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (~50%) yield of an episulfide isomer containing a strained 3-membered ring within ~1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

At the fundamental level, full description of light-matter interaction requires quantum treatment of both matter and light. However, for standard light sources generating intense laser pulses carrying quadrillions of photons in a coherent state, the classical description of light during intense laser-matter interaction has been expected to be adequate. Here we show how nonlinear optical response of matter can be controlled to generate dramatic deviations from this standard picture, including generation of several squeezed and entangled harmonics of the incident laser light. In particular, such non-trivial quantum states of harmonics are generated as soon as one of the harmonics induces a transition between different laser-dressed states of the material system. Such transitions generate an entangled light-matter wavefunction, which can generate quantum states of harmonics even in the absence of a quantum driving field or material correlations. In turn, entanglement of the material system with a single harmonic generates and controls entanglement between different harmonics. Hence, nonlinear media that are near-resonant with at least one of the harmonics appear to be quite attractive for controlled generation of massively entangled quantum states of light. Our analysis opens remarkable opportunities at the interface of attosecond physics and quantum optics, with implications for quantum information science.

It has been shown in \href{this https URL}{\textit{Phys. Rev. Lett.}, \textbf{108} 170402 (2012)}, that quantum tunneling is instantaneous using a time-of-arrival (TOA) operator constructed by Weyl quantization of the classical TOA. However, there are infinitely many possible quantum images of the classical TOA, leaving it unclear if one is uniquely preferred over the others. This raises the question on whether instantaneous tunneling time is simply an artifact of the chosen ordering rule. Here, we demonstrate that tunneling time vanishes for all possible quantum images of the classical arrival time, irrespective of the ordering rule between the position and momentum observables. The result still holds for TOA-operators that are constructed independent of canonical quantization, while still imposing the correct algebra defined by the time-energy canonical commutation relation.

Isotopic substitution in molecular systems can affect fundamental molecular properties including the energy position and spacing of electronic, vibrational and rotational levels, thus modifying the dynamics associated to their coherent superposition. In extreme ultraviolet spectroscopy, the photoelectron leaving the molecule after the absorption of a single photon can trigger an ultrafast nuclear motion in the cation, which can lead, eventually, to molecular fragmentation. This dynamics depends on the mass of the constituents of the cation, thus showing, in general, a significant isotopic dependence. In time-resolved attosecond photoelectron interferometry, the absorption of the extreme ultraviolet photon is accompanied by the exchange of an additional quantum of energy (typically in the infrared spectral range) with the photoelectron-photoion system, offering the opportunity to investigate in time the influence of isotopic substitution on the characteristics of the photoionisation dynamics. Here we show that attosecond photoelectron interferometry is sensitive to isotopic substitution by investigating the two-color photoionisation spectra measured in a mixture of methane (CH$_4$) and deuteromethane (CD$_4$). The isotopic dependence manifests itself in the modification of the amplitude and contrast of the oscillations of the photoelectron peaks generated in the two-color field with the two isotopologues. The observed effects are interpreted considering the differences in the time evolution of the nuclear autocorrelation functions in the two molecules.

We experimentally and numerically investigate self-compression of pulses around 5 $\mu$m wavelength in a noble-gas-filled hollow waveguides. We demonstrate spectral broadening of multi-mJ pulses at 4.9 $\mu$m and associated pulse compression from 85 fs to 47 fs in the solitonic pulse compression regime. The self-compression resulted in sub-three-cycle pulses with 17 GW peak power in the 1-kHz pulse train. A numerical model is established and benchmarked against the experimental results. It allows further insights into the pulse compression process, such as scaling of the compression as a function of gas pressure and waveguide radius, and predicts pulse compression in sub-cycle regime for realistic input parameters.

Photocurrent-induced harmonics appear in gases and solids due to tunnel ionization of electrons in strong fields and subsequent acceleration. In contrast to three-step harmonic emission, no return to the parent ions is necessary. Here we show that the same mechanism produces harmonics in metallic nanostructures in strong fields. Furthermore, we demonstrate how strong local field gradient, appearing as a consequence of the field enhancement, affects photocurrent-induced harmonics. This influence can shed light at the state of electron as it appears in the continuum, in particular, to its initial velocity.

Sub-laser cycle time scale of electronic response to strong laser fields enables attosecond dynamical imaging in atoms, molecules and solids. Optical tunneling and high harmonic generation are the hallmarks of attosecond imaging in optical domain, including imaging of phase transitions in solids. Topological phase transition yields a state of matter intimately linked with electron dynamics, as manifested via the chiral edge currents in topological insulators. Does topological state of matter leave its mark on optical tunneling and sub-cycle electronic response? We identify distinct topological effects on the directionality and the attosecond timing of currents arising during electron injection into conduction bands. We show that electrons tunnel across the band gap differently in trivial and topological phases, for the same band structure, and identify the key role of the Berry curvature in this process. These effects map onto topologically-dependent attosecond delays in high harmonic emission and the helicities of the emitted harmonics, which can record the phase diagram of the system and its topological invariants. Thus, the topological state of the system controls its attosecond, highly non-equilibrium electronic response to strong low-frequency laser fields, in bulk. Our findings create new roadmaps in studies of topological systems, building on ubiquitous properties of sub-laser cycle strong field response - a unique mark of attosecond science.

We propose dynamical Bragg mirrors as a means to compress intense short optical pulses. We show that strong-field photoexcitation of carriers changes the refractive index of the layers and leads to motion of the resonance-defined boundary of the Bragg mirror. In a reflection geometry, this counter-propagating motion leads to significant compression of the incident pulse. We utilize a finite-difference time-domain numerical model to predict up to a 6-fold pulse compression in the few-femtosecond regime. Modification of the refractive index and properties of the compressed pulse as a function of the incident pulse parameters are investigated.

Ultrashort XUV pulses of the Free-Electron-LASer in Hamburg (FLASH) were used to investigate laser-induced fragmentation patterns of the prototypical chiral molecule 1-iodo-2-methyl-butane (C$_5$H$_{11}$I) in a pump-probe scheme. Ion velocity-map images and mass spectra of optical-laser-induced fragmentation were obtained for subsequent FEL exposure with photon energies of 63 eV and 75 eV. These energies specifically address the iodine 4d edge of neutral and singly charged iodine, respectively. The presented ion spectra for two optical pump-laser wavelengths, i.e., 800 nm and 267 nm, reveal substantially different cationic fragment yields in dependence on the wavelength and intensity. For the case of 800-nm-initiated fragmentation, the molecule dissociates notably slower than for the 267-nm pump. The results underscore the importance of considering optical-laser wavelength and intensity in the dissociation dynamics of this prototypical chiral molecule that is a promising candidate for future studies of its asymmetric nature.