D. M. Villeneuve

Tomographic imaging of molecular orbitals

Single-electron wavefunctions, or orbitals, are the mathematical constructs used to describe the multi-electron wavefunction of molecules. Because the highest-lying orbitals are responsible for chemical properties, they are of particular interest. To observe these orbitals change as bonds are formed and broken is to observe the essence of chemistry. Yet single orbitals are difficult to observe experimentally, and until now, this has been impossible on the timescale of chemical reactions. Here we demonstrate that the full three-dimensional structure of a single orbital can be imaged by a seemingly unlikely technique, using high harmonics generated from intense femtosecond laser pulses focused on aligned molecules. Applying this approach to a series of molecular alignments, we accomplish a tomographic reconstruction of the highest occupied molecular orbital of N2. The method also allows us to follow the attosecond dynamics of an electron wave packet.

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.

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.

Laser-Induced Electron Tunneling and Diffraction

Molecular structure is usually determined by measuring the diffraction pattern the molecule impresses on x-rays or electrons. We used a laser field to extract electrons from the molecule itself, accelerate them, and in some cases force them to recollide with and diffract from the parent ion, all within a fraction of a laser period. Here, we show that the momentum distribution of the extracted electron carries the fingerprint of the highest occupied molecular orbital, whereas the elastically scattered electrons reveal the position of the nuclear components of the molecule. Thus, in one comprehensive technology, the photoelectrons give detailed information about the electronic orbital and the position of the nuclei.

Following a chemical reaction using high-harmonic interferometry

The study of chemical reactions on the molecular (femtosecond) timescale typically uses pump laser pulses to excite molecules and subsequent probe pulses to interrogate them. The ultrashort pump pulse can excite only a small fraction of molecules, and the probe wavelength must be carefully chosen to discriminate between excited and unexcited molecules. The past decade has seen the emergence of new methods that are also aimed at imaging chemical reactions as they occur, based on X-ray diffraction, electron diffraction or laser-induced recollision—with spectral selection not available for any of these new methods. Here we show that in the case of high-harmonic spectroscopy based on recollision, this apparent limitation becomes a major advantage owing to the coherent nature of the attosecond high-harmonic pulse generation. The coherence allows the unexcited molecules to act as local oscillators against which the dynamics are observed, so a transient grating technique can be used to reconstruct the amplitude and phase of emission from the excited molecules. We then extract structural information from the amplitude, which encodes the internuclear separation, by quantum interference at short times and by scattering of the recollision electron at longer times. The phase records the attosecond dynamics of the electrons, giving access to the evolving ionization potentials and the electronic structure of the transient molecule. In our experiment, we are able to document a temporal shift of the high-harmonic field of less than an attosecond (1 as = 10−18 s) between the stretched and compressed geometry of weakly vibrationally excited Br2 in the electronic ground state. The ability to probe structural and electronic features, combined with high time resolution, make high-harmonic spectroscopy ideally suited to measuring coupled electronic and nuclear dynamics occurring in photochemical reactions and to characterizing the electronic structure of transition states.

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.

Laser Tunnel Ionization from Multiple Orbitals in HCl

A Lower Tunnel Among the peculiarities inherent in quantum mechanics is the ability of particles to tunnel through barriers that they lack the energy to surmount classically, as happens during radioactive decay. Strong laser fields can liberate electrons in this way from atoms and molecules. Akagi et al. (p. 1364) elegantly confirm that tunneling is not limited to the highest-energy electrons in a system by mapping the energy and momentum of both the ejected electron and positive ion produced when an intense laser pulse impinges on hydrogen chloride. When the molecule adopts specific orientations relative to the laser field, tunneling occurs from lower-lying states, as well as the highest-energy occupied orbital. This raises the possibility of tunneling microscopy capable of imaging the electronic structure of single molecules. Ion imaging shows that electrons can tunnel out of states below the highest occupied orbital of a molecule. Tunneling, one of the most striking manifestations of quantum mechanics, influences the electronic structure of many molecules and solids and is responsible for radioactive decay. Much of the interaction of intense light pulses with matter commences with electrons tunneling from atoms or molecules to the continuum. Until recently, this starting point was assumed to be the highest occupied orbital of a given system. We have now observed tunneling from a lower-lying state in hydrogen chloride (HCl). Analyzing two independent experimental observables allowed us to isolate (via fragment ions), identify (via molecular frame photoelectron angular distributions), and, with the help of ab initio simulations, quantify the contribution of lower-lying orbitals to the total and angle-dependent tunneling current of the molecule. Our results bolster the emerging tenet that the coherent interaction between different orbitals—which can amplify the impact of lower orbitals—must be considered in tunneling processes.

Femtosecond wave‐packet dynamics studied by time‐resolved zero‐kinetic energy photoelectron spectroscopy

Femtosecond pump–probe zero‐kinetic‐energy (ZEKE) photoelectron spectroscopy is studied using the known wave‐packet dynamics of I2 (B state). The 340 fs wave‐packet period, wave‐packet dephasing and rephasing are observed in the ZEKE signal. The effect of various laser and ZEKE parameters on the wave‐packet dynamics is discussed.

Conical Intersection Dynamics in NO2 Probed by Homodyne High-Harmonic Spectroscopy

Coincident vibrational and electronic rearrangements in a photoexcited molecule are tracked in fine detail. Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occur in nitrogen dioxide when a photoexcited wave packet crosses a conical intersection. At longer delays, we observe the onset of statistical dissociation dynamics. The present results demonstrate that high-harmonic spectroscopy could become a powerful tool to highlight electronic dynamics occurring along nonadiabatic chemical reaction pathways.

Compression of 1.8 μm laser pulses to sub two optical cycles with bulk material

We demonstrate a simple scheme to generate 0.4 mJ 11.5 fs laser pulses at 1.8 μm. Optical parametrically amplified pulses are spectrally broadened by nonlinear propagation in an argon-filled hollow-core fiber and subsequently compressed to 1.9 optical cycles by linear propagation through bulk material in the anomalous dispersion regime. This pulse compression scheme is confirmed through numerical simulations.