Search

Intramolecular charge transfer and the associated changes in molecular structure in N,N'-dimethylpiperazine are tracked using femtosecond gas-phase X-ray scattering. The molecules are optically excited to the 3p state at 200 nm. Following rapid relaxation to the 3s state, distinct charge-localized and charge-delocalized species related by charge transfer are observed. The experiment determines the molecular structure of the two species, with the redistribution of electron density accounted for by a scattering correction factor. The initially dominant charge-localized state has a weakened carbon-carbon bond and reorients one methyl group compared with the ground state. Subsequent charge transfer to the charge-delocalized state elongates the carbon-carbon bond further, creating an extended 1.634 Å bond, and also reorients the second methyl group. At the same time, the bond lengths between the nitrogen and the ring-carbon atoms contract from an average of 1.505 to 1.465 Å. The experiment determines the overall charge transfer time constant for approaching the equilibrium between charge-localized and charge-delocalized species to 3.0 ps.

We publish three Roadmaps on photonic, electronic and atomic collision physics in order to celebrate the 60th anniversary of the ICPEAC conference. In Roadmap I, we focus on the light-matter interaction. In this area, studies of ultrafast electronic and molecular dynamics have been rapidly growing, with the advent of new light sources such as attosecond lasers and x-ray free electron lasers. In parallel, experiments with established synchrotron radiation sources and femtosecond lasers using cutting-edge detection schemes are revealing new scientific insights that have never been exploited. Relevant theories are also being rapidly developed. Target samples for photon-impact experiments are expanding from atoms and small molecules to complex systems such as biomolecules, fullerene, clusters and solids. This Roadmap aims to look back along the road, explaining the development of these fields, and look forward, collecting contributions from twenty leading groups from the field.

We have observed details of the internal motion and dissociation channels in photoexcited carbon disulfide (CS2) using time-resolved x-ray scattering (TRXS). Photoexcitation of gas-phase CS2 with a 200 nm laser pulse launches oscillatory bending and stretching motion, leading to dissociation of atomic sulfur in under a picosecond. During the first 300 fs following excitation, we observe significant changes in the vibrational frequency as well as some dissociation of the C–S bond, leading to atomic sulfur in the both 1D and 3P states. Beyond 1400 fs, the dissociation is consistent with primarily 3P atomic sulfur dissociation. This channel-resolved measurement of the dissociation time is based on our analysis of the time-windowed dissociation radial velocity distribution, which is measured using the temporal Fourier transform of the TRXS data aided by a Hough transform that extracts the slopes of linear features in an image. The relative strength of the two dissociation channels reflects both their branching ratio and differences in the spread of their dissociation times. Measuring the time-resolved dissociation radial velocity distribution aids the resolution of discrepancies between models for dissociation proposed by prior photoelectron spectroscopy work. [ABSTRACT FROM AUTHOR]

High-lying electronic states hold the potential for new and unusual photochemical reactions. However, for conventional single-photon excitation in the condensed phase, reaching these states is often not possible because the vacuum-ultraviolet (VUV) light required is competitively absorbed by the surrounding matrix rather than the molecule of interest. Here, this hurdle is overcome by leveraging nonresonant two-photon absorption (2PA) at 265 nm to achieve preferential photolysis of tetrahydrofuran (THF) trapped within a clathrate hydrate network at 77 K. Electron spin resonance (ESR) spectroscopy enables direct observation and identification of otherwise short-lived organic radicals stabilized by the clathrate cages, providing clues into the rapid dynamics that immediately follow photoexcitation. 2PA induces extensive fragmentation of enclathrated THF yielding 1-alkyl, acyl, allyl and methyl radicals—a stark departure from the reactive motifs commonly reported in γ-irradiated hydrates. We speculate on the undetected transient dynamics and explore the potential role of trapped electrons generated from water and THF. This demonstration of nonresonant two-photon chemistry presents an alternative approach to targeted condensed phase photochemistry in the VUV energy range. [ABSTRACT FROM AUTHOR]

We resolve the structural dynamics of the ultrafast photoinduced ring opening reaction of 1,3-cyclohexadiene in space and time employing megaelectronvolt gas phase ultrafast electron diffraction. We, furthermore, observe coherent large amplitude motions of the photoproduct.

Pump-probe gas phase X-ray scattering experiments, enabled by the development of X-ray free electron lasers, have advanced to reveal scattering patterns of molecules far from their equilibrium geometry. While dynamic displacements reflecting the motion of wavepackets can probe deeply into the reaction dynamics, in many systems, the thermal excitation embedded in the molecules upon optical excitation and energy randomization can create systems that encompass structures far from the ground state geometry. For polyatomic molecular systems, large amplitude vibrational motions are associated with anharmonicity and shifts of interatomic distances, making analytical solutions using traditional harmonic approximations inapplicable. More generally, the interatomic distances in a polyatomic molecule are not independent and the traditional equations commonly used to interpret the data may give unphysical results. Here, we introduce a novel method based on molecular dynamic trajectories and illustrate it on two examples of hot, vibrating molecules at thermal equilibrium. When excited at 200 nm, 1,3-cyclohexadiene (CHD) relaxes on a subpicosecond time scale back to the reactant molecule, the dominant pathway, and to various forms of 1,3,5-hexatriene (HT). With internal energies of about 6 eV, the energy thermalizes quickly, leading to structure distributions that deviate significantly from their vibrationless equilibrium. The experimental and theoretical results are in excellent agreement and reveal that a significant contribution to the scattering signal arises from transition state structures near the inversion barrier of CHD. In HT, our analysis clarifies that previous inconsistent structural parameters determined by electron diffraction were artifacts that might have resulted from the use of inapplicable analytical equations. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of 1,4-diiodobenzene is investigated using ultrafast time-resolved photoelectron spectroscopy. Following excitation by laser pulses at 271 nm, the excited-state dynamics is probed by resonance-enhanced multiphoton ionization with 405 nm probe pulses. A progression of Rydberg states, which come into resonance sequentially, provide a fingerprint of the dissociation dynamics of the molecule. The initial excitation decays with a lifetime of 33 ± 4 fs, in good agreement with a previous study. The spectrum is interpreted by reference to ab initio calculations at the CASPT2(18,14) level, including spin-orbit coupling. We propose that both the 5B1 and 6B1 states are excited initially, and based on the calculations, we identify diabatic spin-orbit coupled states corresponding to the main dissociation pathways. [ABSTRACT FROM AUTHOR]

An investigation is conducted on the energy flow and fragmentation dynamics of N,N-dimethylisopropylamine (DMIPA) upon excitation to the 3y Rydberg states with the use of time-resolved photoelectron and mass spectrometry. An ultrafast internal conversion was observed from 3p to 3s proceeding on a scale of 701 plus/minus 45 fs.

A theoretical study of the electron diffraction patterns that from aligning a molecule, s-tetrazine (C2N4H2), in a high intensity laser field using the Friedrich-Herscbach approach is performed. It is suggested that alignment is very beneficial for extracting information from gas-phase diffraction patterns and where detrimental multiphoton processes do not yet compromise the interpretation of the molecular structure.

The changes in electron diffraction patterns were observed on ultrashort time scales upon irradiation of 1,3-cyclohexadiene with femtosecond laser pulse. The internal conversion brings the molecule to a saddle point, from where one pathway leads back to cyclohexadiene, while another generates 1,3,5-hexatriene in one of its isomeric forms.

Research is done on three-photon ionization photoelectron spectra of phenol in a molecular beam. In conclusion further dynamical processes among the Rydberg states occur on a picosecond time scale and time-delayed photoelectron spectra are obtained from two-color ionization experiments.

Research is done on the three-photon ionization pathways o phenol involving the S2 electronic state as well as higher molecular resonances, which are explored. In conclusion, the effect the ionization pathway on the interpretation of time-resolved multiphoton ionization experiments is examined.