Misha Ivanov

High harmonic interferometry of multi-electron dynamics in molecules

High harmonic emission occurs when an electron, liberated from a molecule by an incident intense laser field, gains energy from the field and recombines with the parent molecular ion. The emission provides a snapshot of the structure and dynamics of the recombining system, encoded in the amplitudes, phases and polarization of the harmonic light. Here we show with CO2 molecules that high harmonic interferometry can retrieve this structural and dynamic information: by measuring the phases and amplitudes of the harmonic emission, we reveal ‘fingerprints’ of multiple molecular orbitals participating in the process and decode the underlying attosecond multi-electron dynamics, including the dynamics of electron rearrangement upon ionization. These findings establish high harmonic interferometry as an effective approach to resolving multi-electron dynamics with sub-Ångström spatial resolution arising from the de Broglie wavelength of the recombining electron, and attosecond temporal resolution arising from the timescale of the recombination event.

Electron localization following attosecond molecular photoionization

For the past several decades, we have been able to directly probe the motion of atoms that is associated with chemical transformations and which occurs on the femtosecond (10−15-s) timescale. However, studying the inner workings of atoms and molecules on the electronic timescale has become possible only with the recent development of isolated attosecond (10−18-s) laser pulses. Such pulses have been used to investigate atomic photoexcitation and photoionization and electron dynamics in solids, and in molecules could help explore the prompt charge redistribution and localization that accompany photoexcitation processes. In recent work, the dissociative ionization of H2 and D2 was monitored on femtosecond timescales and controlled using few-cycle near-infrared laser pulses. Here we report a molecular attosecond pump–probe experiment based on that work: H2 and D2 are dissociatively ionized by a sequence comprising an isolated attosecond ultraviolet pulse and an intense few-cycle infrared pulse, and a localization of the electronic charge distribution within the molecule is measured that depends—with attosecond time resolution—on the delay between the pump and probe pulses. The localization occurs by means of two mechanisms, where the infrared laser influences the photoionization or the dissociation of the molecular ion. In the first case, charge localization arises from quantum mechanical interference involving autoionizing states and the laser-altered wavefunction of the departing electron. In the second case, charge localization arises owing to laser-driven population transfer between different electronic states of the molecular ion. These results establish attosecond pump–probe strategies as a powerful tool for investigating the complex molecular dynamics that result from the coupling between electronic and nuclear motions beyond the usual Born–Oppenheimer approximation.

Sub-laser-cycle electron pulses for probing molecular dynamics

Experience shows that the ability to make measurements in any new time regime opens new areas of science. Currently, experimental probes for the attosecond time regime (10-18–10-15 s) are being established. The leading approach is the generation of attosecond optical pulses by ionizing atoms with intense laser pulses. This nonlinear process leads to the production of high harmonics during collisions between electrons and the ionized atoms. The underlying mechanism implies control of energetic electrons with attosecond precision. We propose that the electrons themselves can be exploited for ultrafast measurements. We use a ‘molecular clock’, based on a vibrational wave packet in H2+ to show that distinct bunches of electrons appear during electron–ion collisions with high current densities, and durations of about 1 femtosecond (10-15 s). Furthermore, we use the molecular clock to study the dynamics of non-sequential double ionization.

Probing molecular dynamics with attosecond resolution using correlated wave packet pairs

Spectroscopic measurements with increasingly higher time resolution are generally thought to require increasingly shorter laser pulses, as illustrated by the recent monitoring of the decay of core-excited krypton using attosecond photon pulses. However, an alternative approach to probing ultrafast dynamic processes might be provided by entanglement, which has improved the precision of quantum optical measurements. Here we use this approach to observe the motion of a D2+ vibrational wave packet formed during the multiphoton ionization of D2 over several femtoseconds with a precision of about 200 attoseconds and 0.05 ångströms, by exploiting the correlation between the electronic and nuclear wave packets formed during the ionization event. An intense infrared laser field drives the electron wave packet, and electron recollision probes the nuclear motion. Our results show that laser pulse duration need not limit the time resolution of a spectroscopic measurement, provided the process studied involves the formation of correlated wave packets, one of which can be controlled; spatial resolution is likewise not limited to the focal spot size or laser wavelength.

Resolving the time when an electron exits a tunnelling barrier

The tunnelling of a particle through a barrier is one of the most fundamental and ubiquitous quantum processes. When induced by an intense laser field, electron tunnelling from atoms and molecules initiates a broad range of phenomena such as the generation of attosecond pulses, laser-induced electron diffraction and holography. These processes evolve on the attosecond timescale (1 attosecond ≡ 1 as = 10−18 seconds) and are well suited to the investigation of a general issue much debated since the early days of quantum mechanics—the link between the tunnelling of an electron through a barrier and its dynamics outside the barrier. Previous experiments have measured tunnelling rates with attosecond time resolution and tunnelling delay times. Here we study laser-induced tunnelling by using a weak probe field to steer the tunnelled electron in the lateral direction and then monitor the effect on the attosecond light bursts emitted when the liberated electron re-encounters the parent ion. We show that this approach allows us to measure the time at which the electron exits from the tunnelling barrier. We demonstrate the high sensitivity of the measurement by detecting subtle delays in ionization times from two orbitals of a carbon dioxide molecule. Measurement of the tunnelling process is essential for all attosecond experiments where strong-field ionization initiates ultrafast dynamics. Our approach provides a general tool for time-resolving multi-electron rearrangements in atoms and molecules—one of the key challenges in ultrafast science.

Polyatomic molecules in strong laser fields: Nonadiabatic multielectron dynamics

We report the observation and characterization of a new nonresonant strong field ionization mechanism in polyatomic molecules: Nonadiabatic multi-electron (NME) dynamics. The strong field response of a given molecule depends on important properties such as molecular geometry and bonding, the path length of delocalized electrons and/or ionization potential as well as on basic laser pulse parameters such as wavelength and intensity. Popular quasi-static tunnelling models of strong field molecular ionization, based upon the adiabatic response of a single active electron, are demonstrated to be inadequate when electron delocalization is important. The NME ionization mechanism greatly affects molecular ionization, its fragmentation and its energetics. In addition, multi-electron effects are shown to be present even in the adiabatic long wavelength limit.

Enhanced phase-matching for generation of soft X-ray harmonics and attosecond pulses in atomic gases

Focus Serial: Frontiers of Nonlinear Optics We theoretically investigate the generation of high harmonics and attosecond pulses by mid-infrared (IR) driving fields. Conditions for coherent build-up of high harmonics are revisited. We show that the coherence length dictated by ionization-induced dephasing does not constitute an ultimate limitation to the coherent growth of soft X-ray (> 100 eV) harmonics driven by few-cycle mid-IR driving pulses: perfect phase-matching, similar to non-adiabatic self-phase- matching, can be achieved even without non-linear deformation of the driving pulse. Our trajectory-based analysis of phase-matching reveals several important advantages of using longer laser wavelengths: conversion efficiency can be improved by orders of magnitude, phase-matched build-up of harmonics can be achieved in a jet with a high gas pressure, and isolated attosecond pulses can be extracted from plateau harmonics.

Anatomy of strong field ionization

Strong field ionization is a starting point for a rich set of physical phenomena associated with attosecond  science. This paper provides an introductory overview of the basic theory of strong field ionization and focuses on (i) the physics and the dynamics of the electron transition to the continuum, and (ii) the shape of the electron wavepacket as it appears in the continuum.

Reading diffraction images in strong field ionization of diatomic molecules

We present a theoretical analysis of how intense, few-cycle infrared laser pulses can be used to image the structure of small molecules with nearly 1 fs temporal and sub-A spatial resolution. We identify and analyse several physical mechanisms responsible for the distortions of the diffraction image and describe a recipe for recovering an un-distorted image from angle and energy-resolved electron spectra. We also identify holographic patterns in the photoelectron spectra and discuss the requirements to enhancing the hologram resolution for imaging the scattering potential.

Generating Isolated Elliptically Polarized Attosecond Pulses Using Bichromatic Counterrotating Circularly Polarized Laser Fields

We theoretically demonstrate the possibility to generate both trains and isolated attosecond pulses with high ellipticity in a practical experimental setup. The scheme uses circularly polarized, counterrotating two-color driving pulses carried at the fundamental and its second harmonic. Using a model Ne atom, we numerically show that highly elliptic attosecond pulses are generated already at the single-atom level. Isolated pulses are produced by using few-cycle drivers with controlled time delay between them.