Search

We use covariance velocity map imaging of fragment ions from the strong field double ionization of formaldehyde in conjunction with trajectory surface hopping calculations to determine the ionization yields to different singlet and triplet states of the dication. The calculated kinetic energy release for trajectories initiated on different electronic states is compared with the experimental values based on momentum resolved covariance measurements. We determine the state resolved double ionization yields as a function of laser intensity and pulse duration down to 6 fs (two optical cycles).

Nonadiabatic excited state dynamics are important in a variety of processes. Theoretical and experimental developments have allowed for a great progress in this area, while combining the two is often necessary and the best approach to obtain insight into the photophysical behavior of molecules. In this Feature Article we use examples of our recent work combining time-resolved photoelectron spectroscopy with theoretical nonadiabatic dynamics to highlight important lessons we learned. We compare the nonadiabatic excited state dynamics of three different organic molecules with the aim of elucidating connections between structure and dynamics. Calculations and measurements are compared for uracil, 1,3-cyclooctadiene, and 1,3-cyclohexadiene. The comparison highlights the role of rigidity in influencing the dynamics and the difficulty of capturing the dynamics accurately with calculations.

We extend covariance velocity map ion imaging to four particles, establishing cumulant mapping and allowing for measurements that provide insights usually associated with coincidence detection, but at much higher count rates. Without correction, a fourfold covariance analysis is contaminated by the pairwise correlations of uncorrelated events, but we have addressed this with the calculation of a full cumulant, which subtracts pairwise correlations. We demonstrate the approach on the four-body breakup of formaldehyde following strong field multiple ionization in few-cycle laser pulses. We compare Coulomb explosion imaging for two different pulse durations (30 and 6 fs), highlighting the dynamics that can take place on ultrafast timescales. These results have important implications for Coulomb explosion imaging as a tool for studying ultrafast structural changes in molecules, a capability that is especially desirable for high-count-rate x-ray free-electron laser experiments.

Unusual trapping of an excited state of a dication observed after strong field ionization. Symmetry is responsible for forbidden nonradiative and radiative decay.

We demonstrate the applicability of covariance analysis to three-dimensional velocity-map imaging experiments using a fast time stamping detector. Studying the photofragmentation of strong-field doubly ionized D2O molecules, we show that combining high count rate measurements with covariance analysis yields the same level of information typically limited to the “gold standard” of true, low count rate coincidence experiments, when averaging over a large ensemble of photofragmentation events. This increases the effective data acquisition rate by approximately 2 orders of magnitude, enabling a new class of experimental studies. This is illustrated through an investigation into the dependence of three-body D2O2+ dissociation on the intensity of the ionizing laser, revealing mechanistic insights into the nuclear dynamics driven during the laser pulse. The experimental methodology laid out, with its drastic reduction in acquisition time, is expected to be of great benefit to future photofragment imaging studies.

We present a simple approach to characterize the spatial variation of the gain in microchannel plate (MCP) coupled to phosphor detectors using single electron or photon hits. The technique is easy to implement and general enough to be extended to other kinds of detectors. We demonstrate the efficacy of the approach on both laboratory and Monte Carlo generated datasets. Furthermore, we use the approach to measure the variation in gain over time as the MCP is exposed to an increasing number of electrons.

The structural dynamics of photoexcited gas-phase carbon disulfide (CS

The structural dynamics of photoexcited gas-phase carbon disulfide (CS2) molecules are investigated using ultrafast electron diffraction. The dynamics were triggered by excitation of the optically bright 1B2(1Σu+) state by an ultraviolet femtosecond laser pulse centred at 200 nm. In accordance with previous studies, rapid vibrational motion facilitates a combination of internal conversion and intersystem crossing to lower-lying electronic states. Photodissociation via these electronic manifolds results in the production of CS fragments in the electronic ground state and dissociated singlet and triplet sulphur atoms. The structural dynamics are extracted from the experiment using a trajectory-fitting filtering approach, revealing the main characteristics of the singlet and triplet dissociation pathways. Finally, the effect of the time-resolution on the experimental signal is considered and an outlook to future experiments provided.

We compare different levels of theory for simulating excited state molecular dynamics and use time-resolved photoelectron spectroscopy measurements to benchmark the theory. We perform trajectory surface hopping simulations for uracil excited to the first bright state (ππ*) using three different levels of theory (CASSCF, MRCIS, and XMS-CASPT2) in order to understand the role of dynamical correlation in determining the excited state dynamics, with a focus on the coupling between different electronic states and internal conversion back to the ground state. These dynamics calculations are used to simulate the time-resolved photoelectron spectra. The comparison of the calculated and measured spectra allows us to draw conclusions regarding the relative insights and quantitative accuracy of the calculations at the three different levels of theory, demonstrating that detailed quantitative comparisons of time-resolved photoelectron spectra can be used to benchmark methodology.

Time-resolved photoionization measurements were performed on o-nitrophenol pumped with UV laser pulses at a central wavelength of 255 nm (4.9 eV) and probed with vacuum ultraviolet (VUV) pulses at 153 nm (8.1 eV). The photoelectron spectrum and time of flight mass spectrum for ions were recorded at each pump–probe delay. The measurements are interpreted with the aid of electronic structure calculations for both the neutral and ionic states. Evidence is found for the formation of a bicyclic intermediate followed by NO dissociation through a process of internal conversion and intersystem crossing. The combination of photoelectron and photoion spectroscopy, together with computational results, provides strong evidence of intersystem crossing that is difficult to establish with only a single technique.

Electronic and nuclear dynamics in one Because of the complex, ultrafast interplay between nuclear and electronic degrees of freedom, probing both nuclear and electronic dynamics in excited electronic states within a single time-resolved experiment is a great challenge. Yang et al. used ultrafast electron diffraction in combination with ab initio nonadiabatic molecular dynamics and diffraction simulations to study the relaxation dynamics of isolated pyridine molecules after photoexcitation to the S 1 state (see the Perspective by Domcke and Sobolewski). They showed that electronic state evolution and molecular structural changes can be recorded simultaneously and independently by tracing a transient signal in small-angle inelastic scattering and large-angle elastic diffraction, respectively. Science , this issue p. 885 ; see also p. 820

We demonstrate three-dimensional velocity map imaging of low energy electrons using a TPX3CAM, where the three-dimensional momentum information [p

We demonstrate an enhancement in the formation of D2O3+ as a consequence of field-free molecular dynamics following the strong-field multiple ionization of deuterated water via 6-fs 800-nm pulse pairs.

We develop mathematical tools to compute higher order covariances in charged particle detection, and demonstrate fourfold covariance measurements for molecular imaging with intense ultrafast laser pulses.

We use an acousto-optic modulator based pulse shaper to compress octave-spanning pulses from a stretched hollow-core fiber, characterize the pulses through a pulse shaper assisted version of dispersion scans, and shape the pulses for time resolved measurements of molecular dynamics.

We carry out strong field double ionization measurements of deuterated formaldehyde using covariance velocity map imaging. Comparing our measurements with trajectory surface hopping calculations, we find that we produce a surprising distribution of dicationic states.

We compare time resolved photoelectron spectroscopy measurements and trajectory surface hopping calculations for 1,3 - Cyclohexadiene (CHD) and cis,cis-1,3 - Cyclooctadiene (COD). We find qualitative agreement between experiment and theory for both but quantitative agreement only for CHD.

We develop a technique to resolve photoelectron momenta in 3 dimensions using a fast event-based camera (TPX3CAM). Our method is versatile and can be readily implemented in most velocity map imaging systems. We demonstrate this capability in the example of above threshold ionization of Xenon.

Since its inception, velocity map imaging (VMI) has been a powerful tool for measuring the 2D momentum distribution of photoelectrons generated by strong laser fields. There has been continued interest in expanding it into 3D measurements either through reconstructive or direct methods. Recently much work has been devoted to the latter of these, particularly by relating the electron time-of-flight (TOF) to the third momentum component. The technical challenge here is having timing resolution sufficient to resolve structure in the narrow (< 10 ns) electron TOF spread. Here we build upon work in the fields of VMI lens design and 3D VMI measurement by using a plano-convex thick-lens VMI in conjunction with an event-driven camera (TPX3CAM) providing TOF information for high resolution 3D electron momentum measurements. We perform simulations to show that, with the addition of a mesh electrode to the thick-lens VMI geometry, a plano-convex electrostatic field is formed which extends the detectable electron cutoff energy range while retaining high resolution. Further, the thick-lens also extends the electron TOF range which allows for better resolution of the momentum along this axis. We experimentally demonstrate these capabilities by examining above-threshold ionization in Xenon where the apparatus is shown to collect electrons of energy up to $\sim$7 eV with a TOF spread of $\sim$30 ns, both of which are improvements on previous work by factors of $\sim$1.4 and $\sim$3.75 respectively. Finally, the PCTL-VMI is equipped with a coincident ion TOF spectrometer which is shown to effectively extract unique 3D momentum distributions for different ionic species within a gas mixture. These techniques have potential to lend themselves to more advanced measurements, particularly involving systems where the electron momentum distributions possess non-trivial symmetries and require high resolution.

We demonstrate the applicability of covariance analysis to three-dimensional velocity-map imaging experiments using a fast time stamping detector. Studying the photofragmentation of strong-field doubly ionized D

We investigate the role of nuclear motion and strong-field-induced electronic couplings during the double ionization of deuterated water using momentum-resolved coincidence spectroscopy. By examining the three-body dicationic dissociation channel, D$^{+}$/D$^{+}$/O, for both few- and multi-cycle laser pulses, strong evidence for intra-pulse dynamics is observed. The extracted angle- and energy-resolved double ionization yields are compared to classical trajectory simulations of the dissociation dynamics occurring from different electronic states of the dication. In contrast with measurements of single photon double ionization, pronounced departure from the expectations for vertical ionization is observed, even for pulses as short as 10~fs in duration. We outline numerous mechanisms by which the strong laser field can modify the nuclear wavefunction en-route to final states of the dication where molecular fragmentation occurs. Specifically, we consider the possibility of a coordinate-dependence to the strong-field ionization rate, intermediate nuclear motion in monocation states prior to double ionization, and near-resonant laser-induced dipole couplings in the ion. These results highlight the fact that, for small and light molecules such as D$_2$O, a vertical-transition treatment of the ionization dynamics is not sufficient to reproduce the features seen experimentally in the strong field coincidence double-ionization data., Comment: 14 pages, 13 figures

Following the coupled motion of electrons and nuclei in molecules is difficult if one uses time-resolved approaches that only provide direct information on one or the other. We combine two complementary measurements, Time- Resolved Photoelectron/PhotoIon Spectroscopy (TRPES and TRPIS) and Ultrafast Electron Diffraction, to follow the electronic and nuclear dynamics of gas phase CH2I2 when exposed to UV light. In order to interpret the measurement, trajectory surface hopping calculations are carried out and all the measurement observables are simulated and directly compared with the measurement signals. Our measurements highlight the coupled electron-nucleus dynamics that allow for electronic potential energy to be converted into nuclear kinetic energy as well as complicated structural rearrangements of the molecule that involve symmetry breaking, dissociation, rotation, and non-local wave-packet dynamics., Ultrafast Nonlinear Imaging and Spectroscopy IX, August 1-5, 2021, San Diego, United States, Series: Proceedings of SPIE

Polyatomic molecules in strong laser fields can undergo substantial nuclear motion within tens of femtoseconds. Ion imaging methods based on dissociation or Coulomb explosion therefore have difficulty faithfully recording the geometry dependence of the field ionization that initiates the dissociation process. Here we compare the strong-field double ionization and subsequent dissociation of water (both H$_2$O and D$_2$O) in 10-fs and 40-fs 800-nm laser pulses. We find that 10-fs pulses turn off before substantial internuclear motion occurs, whereas rapid internuclear motion can take place during the double ionization process for 40-fs pulses. The short-pulse measurements are consistent with a simple tunnel ionization picture, whose predictions help interpret the motion observed in the long-pulse measurements., 9 pages, 5 figures

The authors show theoretically and experimentally how the time-varying phase or frequency of a chirped strong-field ultrafast laser pulse can be used to control the ionization yield to different ionic states in a polyatomic molecule. The results are interpreted in terms of a competition between two types of nonadiabatic dynamics: multiphoton resonance and internal conversion.

We explore the validity of adiabatic elimination in the derivation of an essential-states representation of the time-dependent Schr\"odinger equation in the presence of a strong laser field. We consider the elimination of off-resonant states in generating an effective two-level description of the light-matter interaction, where the initial and final states are two-photon resonant. The treatment is nonperturbative and can be generalized to $N$-photon absorption.

We perform time-resolved ionization spectroscopy measurements of the excited state dynamics of CH

In this work, we experimentally study the angle-dependent single ionization of carbon dioxide (CO2) by linearly and circularly polarized pulses. The angle dependence of the ionization probability by linearly polarized pulses extracted from time-domain measurements on an impulsively excited rotational wave packet is compared with data obtained from a direct angle-scan measurement. The results from the measurement with linear and circular polarization are consistent with the adiabatic ionization approximation. We extend the time-domain method to extract the dependence of the asymptotic momentum distribution of fragment ions on the orientation of the molecular axis, and apply it to investigate dissociative double ionization of CO2. We show that such measurements can directly test the validity of the axial recoil approximation.

Pump-probe measurements aim to capture the motion of electrons and nuclei on their natural timescales (femtoseconds to attoseconds) as chemical and physical transformations take place, effectively making “molecular movies” with short light pulses. However, the quantum dynamics of interest are filtered by the coordinate-dependent matrix elements of the chosen experimental observable. Thus, it is only through a combination of experimental measurements and theoretical calculations that one can gain insight into the internal dynamics. Here, we report on a combination of structural (relativistic ultrafast electron diffraction, or UED) and spectroscopic (time-resolved photoelectron spectroscopy, or TRPES) measurements to follow the coupled electronic and nuclear dynamics involved in the internal conversion and photodissociation of the polyatomic molecule, diiodomethane (CH_{2}I_{2}). While UED directly probes the 3D nuclear dynamics, TRPES only serves as an indirect probe of nuclear dynamics via Franck-Condon factors, but it is sensitive to electronic energies and configurations, via Koopmans’ correlations and photoelectron angular distributions. These two measurements are interpreted with trajectory surface hopping calculations, which are capable of simulating the observables for both measurements from the same dynamics calculations. The measurements highlight the nonlocal dynamics captured by different groups of trajectories in the calculations. For the first time, both UED and TRPES are combined with theory capable of calculating the observables in both cases, yielding a direct view of the structural and nonadiabatic dynamics involved.

We demonstrate coherent control over internal conversion during strong-field molecular ionization with shaped, few-cycle laser pulses. The control is driven by interference in different neutral states, which are coupled via non-Born-Oppenheimer terms in the molecular Hamiltonian. Our measurements highlight the preservation of electronic coherence in nonadiabatic transitions between electronic states.

We demonstrate spectral broadening and compression of amplified pulses from a titanium sapphire laser system using an argon-filled stretched, hollow-core fiber and an acousto-optic modulator based pulse-shaper. We characterize the pulses using pulse-shaper assisted collinear frequency resolved optical gating, pulse-shaper assisted D-scans, and D-scans using a variable path length water cell. The different compression and characterization approaches consistently compress the pulses down to < 6 fs, less than ∼1 fs from the transform limit. We discuss prospects for pulse shape spectroscopy with these broadband pulses, given our control over the spectral amplitude and phase.

Strong-field ionization plays a fundamental role in attosecond science as the source of electron wave packets which ultimately provide attosecond bursts of radiation as they are driven back to the atom or molecule of origin. Double ionization is an important probe of electron correlation (correlated electron dynamics), which lies at the core of attosecond science. While double ionization of atoms has been studied extensively, the double ionization of molecules is relatively unexplored---particularly for the case of polyatomic systems. We present coincidence (three and four particle) velocity map imaging measurements of molecular double ionization in 1,3-cyclohexadiene and 1,4-cyclohexadiene using few cycle ($\ensuremath{\sim}10$ fs) laser pulses. Our measurements allow us to distinguish between dissociative and nondissociative double ionization, and we find a difference in the correlation of electrons that come from the different channels.

We compare the excited state dynamics of diiodomethane (CH

We study strong field double ionization of a series of organic molecules by making use of coincidence detection of fragment ions. We measure the double ionization yield as a function of pulse duration, intensity, polarization, and molecular conjugation. For conjugated molecules we find strong enhancement in the double ionization rate over what one would expect on the basis of tunneling or multiphoton ionization rates. Calculations reveal a correlation between the electronic structure of the different molecules and the observed double ionization yields, highlighting the removal of electrons from inner orbitals.

We have performed trajectory surface hopping dynamics for cis,cis-1,3-cyclooctadiene to investigate the photochemical pathways involved after being excited to the S1 state. Our calculations reveal ultrafast decay to the ground state, facilitated by conical intersections involving distortions around the double bonds. The main distortions are localized on one double bond, involving twisting and pyramidalization of one of the carbons of that double bond (similar to ethylene), while a limited number of trajectories decay via delocalized (non-local) twisting of both double bonds. The interplay between local and non-local distortions is important in our understanding of photoisomerization in conjugated systems. The calculations show that a broad range of the conical intersection seam space is accessed during the non-adiabatic events. Several products formed on the ground state have also been observed.