In this study, a reaction microscope is used to explore the behavior of electrons in shaped beams under strong field conditions. Photoelectron momentum spectra indicate that the inclusion of orbital angular momentum (OAM) of light does not significantly impact the available electron angular momentum states. However, the distinctive donut shape of the beam plays a crucial role in determining the observed Photoelectron Angular Distributions (PADs). TDSE simulations, incorporating focal volume averaging indicates that the geometric properties of the focal region of the OAM and the Gaussian beams affect the photoelectron spectra differently. By averaging the spectra across different intensity regions, we have provided a qualitative explanation for the variations in photoelectron spectra resulting from the shapes of the individual beams. This result shows that the transfer of OAM in ultrashort light pulses cannot be detected in gas ensembles due to the ionization being overwhelmed by atoms in the most intense region with minimal spatial phase variation within the laser field. We demonstrate that the differences in the momentum spectra arising from shaped beams can be qualitatively explained using models that incorporate the spatial averaging of the beam, rather than focusing on the OAM content.

We investigate the photoinduced dissociation reaction of NO2 -> NO + O upon electronic excitation of the X2A1 (D0) to the A2B2 (D1) state by femtosecond X-ray absorption spectroscopy at the nitrogen K-edge. We obtain key insight into the chemical bond breaking event and its associated electronic structural dynamics. Calculations of the photoinduced reaction allow to assign the transient absorption features at time scales of 10-50 fs to wave packet motions in the excited D1 and ground D0 states, followed by the formation of the NO photoproduct with a 255 +/- 23 fs time constant. Our analysis shows that there is no direct correlation between the 1s core levels and the electronic ground and excited states transition energies and the bond elongation of NO2, while en route to dissociation toward the NO + O photoproducts, in the transient nitrogen K-edge spectra. However, simulations predict that for a sufficiently short UV pump pulse, the early wave packet dynamics in the D1 electronic excited state occurring within the first 35 fs along the bending and symmetric stretching modes can be directly mapped in the transient X-ray absorption spectra.

The three-body dissociation dynamics of the dicationic camphor molecule (C10H16O2+) resulting from Auger decay are investigated using soft x-ray synchrotron radiation. A photoelectron-photoion-photoion coincidence method, a combination of a velocity map imaging spectrometer and a time-of-flight spectrometer is employed to measure the 3D momenta of ions detected in coincidence. The ion mass spectra and the ion-ion coincidence map at photon energies of 287.9 eV (below the C 1s ionization potential) and 292.4 eV (above the C 1s ionization potential for skeletal carbon) reveal that fragmentation depends on the final dicationic state rather than the initial excitation. Using the native frame method, three new fragmentation channels are discussed; (1) CH2CO+ + C7H11+ + CH3, (2) CH3+ + C7H11+ + CH2CO, and (3) C2H5+ + C6H9+ + CH2CO. The dominating nature of sequential decay with deferred charge separation is clearly evidenced in all three channels. The results are discussed based on the experimental angular distributions and momenta distributions, corroborated by geometry optimization of the ground, monocationic, and dicationic camphor molecule.

We investigate the ionisation and fragmentation dynamics of free camphor molecules and camphor-doped helium nanodroplets by extreme ultraviolet (EUV) and soft x-ray photons using velocity map imaging combined with photoelectron-photoion coincidence (VMI-PEPICO) spectroscopy. We notably find that the Penning ionisation of camphor in He nanodroplets at h nu=21.43 eV is soft with nearly identical Penning ionised electron spectra correlated to different molecular fragments. Further, fragmentation following ionisation at all photon energies exhibit a droplet-specific mass peak equivalent to the missing mass of CO, suggesting suppression of further fragmentation inside the droplet. This work reveals unusual features of photoionisation of organic molecules doped in He nanodroplet motivating further experimental and theoretical explorations.

The fragmentation dynamics of the gas-phase, doubly charged camphor molecule, formed by Auger decay following carbon 1s ionisation, using soft X-ray synchrotron radiation, is presented in this work. The technique of velocity map imaging combined with a photoelectron-photoion-photoion coincidence (VMI-PEPIPICO) is used for both electron energy and ion momentum (in-sequence) measurements. The experimental study is complemented by molecular dynamics simulation, performed with an NVT (moles, volume, and temperature) ensemble. Velocity Verlet algorithms were used for time integration at various internal energies. These simulations validate observed dissociation pathways. From these, we successfully deduce that the internal energy of the doubly charged molecular ion has a significant contribution to the fragmentation mechanism. Notably, a prominent signature of the internal energy was observed in the experimentally determined energies of the neutral fragment in these deferred charge separation pathways, entailing a more detailed theoretical study to uncover the exact dissociation dynamics.

Light-matter interaction with laser pulses endowed with orbital angular momentum (OAM) raises a fundamental question about the nature of the transfer of this property of light to matter. In this work, a "reaction microscope" is used for precise measurement of the momentum of ionized photoions and photoelectrons from the interaction of Ar atoms with a linearly polarized, ultrashort (similar to 25 fs), moderately intense (10(13)-10(14) W/cm(2)) OAM carrying laser pulses. The angle and energy-resolved photoelectron spectrum is compared with the photoelectron spectrum obtained from the interaction with the laser beams with no OAM at similar intensities. No evidence of angular momentum transfer to the electrons from light is observed in our experiment.

We report on the fragmentation of multiply charged CH3I ions through dissociative ionization and Coulomb explosion induced by moderately intense (1012-1013 W/cm(2)) ultrashort laser fields. Velocity map imaging of the fragment ions as a function of pulse duration, ranging from 25 fs to 1.5 ps, leads to kinetic energies, angular distributions, and the relative ion yield in different channels of these fragments. We propose possible pathways for the fragmentation channels based on the kinetic energies and theoretical potential energy curves. For the energetic fragments, we observe an enhanced yield with increasing pulse duration. A simple one-dimensional classical model of wave-packet propagation over the proposed intermediate state potential energy curve is used to estimate the ionization probability as a function of pulse duration. Our results suggest that a delayed enhanced ionization is a consequence of rearrangement of the energies of the molecular orbitals following bond stretching. The resultant energy upshift of the inner orbitals at larger internuclear separation gives rise to resonant multiorbital coupling at a critical distance, which enables enhanced ionization for longer pulses.

Fragmentation of CO24+, created by the impact of slow, highly charged ions (96 keV Arq+; 8 <= q <= 14) on CO2, has been studied by recoil ion momentum spectrometry. CO24+ was found to dissociate into three ionic fragments through two channels: CO24+ -> O+ + C2+ + O+ [the (1,2,1) channel] and CO24+ -> O2+ + C+ + O+ [the (2,1,1) channel]. The kinetic energy of each fragment ion and the total kinetic energy release (KER) distributions for these channels were derived. Ab initio quantum chemical calculations at the multiconfiguration self-consistent-field configuration-interaction level of theory were carried out to obtain the potential energy curves of CO24+, from which the expected KER values were derived. A comparison of the experimental KER distributions with the expected KER values for different excited states enabled the estimation of the relative probabilities of accessing different electronic states of CO24+. These probabilities were found to depend on the projectile charge q. The fragmentation was visualized using the Dalitz plots, which revealed that the (1,2,1) channel arises exclusively via concerted fragmentation, while the (2,1,1) channel also has a small contribution from sequential fragmentation.

The acetylene-vinylidene system serves as a benchmark for investigations of ultrafast dynamical processes where the coupling of the electronic and nuclear degrees of freedom provides a fertile playground to explore the femto- and sub-femto-second physics with coherent extreme-ultraviolet (EUV) photon sources both on the table-top as well as free-electron lasers. We focus on detailed investigations of this molecular system in the photon energy range 19-40 eV where EUV pulses can probe the dynamics effectively. We employ photoelectron-photoion coincidence (PEPICO) spectroscopy to uncover hitherto unrevealed aspects of this system. In this work, the role of excited states of the C2H2+ cation, the primary photoion, is specifically addressed. From photoelectron energy spectra and angular distributions, the nature of the dissociation and isomerization channels is discerned. Exploiting the 4π-collection geometry of the velocity map imaging spectrometer, we not only probe pathways where the efficiency of photoionization is inherently high but also perform PEPICO spectroscopy on relatively weak channels.

Molecules ionized by intense (10-100 TW/cm2) and ultrashort (tens of femtoseconds) laser fields undergo rotation and alignment mediated through their polarizability. The expected alignment is indeed observed in the case of O2 molecules ionized by intense laser pulses of 800 nm wavelength and 25 fs duration, as observed through velocity imaging of the fragments. Strikingly, when 35 fs pulses of 400 nm wavelength of comparable intensity are employed, an anomalous hindering of this alignment is observed. In both cases, we propose dissociation pathways for the energetic ions consistent with the recorded kinetic energy distributions. Using a semiclassical model of induced rotation of the molecular ion that involves polarizabilities of the participating excited states, both behaviors are reproduced. The model suggests that the difference in the observations can be attributed to a transient negative polarizability in an intermediate state of the proposed pathway.

A three-dimensional ion imaging spectrometer has been designed and calibrated by ion trajectories simulations. We present a recipe for the verification of the calibration by obtaining kinetic energy (KE) distribution from the recorded flight times alone and consequently correlating the two KE spectra.