We investigate the photodynamics of the 2-methylallyl radical by femtosecond time-resolved photoelectron imaging. The experiments are accompanied by field-induced surface hopping dynamics calculations and the simulation of time-resolved photoelectron intensities and anisotropies, giving insight into the photochemistry and nonradiative relaxation of the radical. 2-methylallyl is excited at 236 nm, 238 nm, and 240.6 nm into a 3p Rydberg state, and the subsequent dynamics is probed by multiphoton ionization using photons of 800 nm. The photoelectron image exhibits a prominent band with considerable anisotropy, which is compatible with the result of theory. The simulations show that the initially excited 3p state is rapidly depopulated to a 3s Rydberg state, from which photoelectrons of high anisotropy are produced. The 3s state then decays within several 100 fs to the D (nπ) state, followed by the deactivation of the D to the electronic ground state on the ps time scale.

We investigated the excited-state dynamics of para-xylylene using a combination of field-induced surface hopping (FISH) simulations and time-resolved ionisation experiments. Our simulations predict an ultrafast decay of the initially excited bright state (S2/S3) to the S1 state on a sub-100 fs time scale, followed by return to the ground state within ∼1 ps. This is accompanied by a transient change of the biradical character of the molecule, as monitored by calculating natural orbital occupation numbers. Specifically, the initially low biradicality is increased by electronic excitation as well as by vibrational activation. Experimentally, para-xylylene was generated by pyrolysis from [2,2]paracyclophane and excited with 266 nm radiation into the S2/S3 bright state. The subsequent dynamics were followed using ionisation as the probe step, with both mass spectra and photoelectron spectra recorded as a function of pump-probe delay. The observed decay of photoelectron and photoion intensities closely matches the theoretical predictions and is consistent with the sequential mechanism found in the simulations. This mechanism exhibits characteristic signatures in both time-resolved mass and photoelectron spectra, in particular in the appearance of fragment ions that are exclusively generated from the S1 state. This allows for a separation of the S2 and S1 dynamics in the photoelectron and mass spectra. An excellent agreement between the observed and the simulated ion signal is observed.

Reactive hydrocarbon molecules like radicals, biradicals and carbenes are not only key players in combustion processes and interstellar and atmospheric chemistry, but some of them are also important intermediates in organic synthesis. These systems typically possess many low-lying, strongly coupled electronic states. After light absorption, this leads to rich photodynamics characterized by a complex interplay of nuclear and electronic motion, which is still not comprehensively understood and not easy to investigate both experimentally and theoretically. In order to elucidate trends and contribute to a more general understanding, we here review our recent work on excitedstate dynamics of open-shell hydrocarbon species using time-resolved photoelectron spectroscopy and field-induced surface hopping simulations, and report new results on the excited-state dynamics of the tropyl and the 1-methylallyl radical. The different dynamics are compared, and the difficulties and future directions of time-resolved photoelectron spectroscopy and excited state dynamics simulations of open-shell hydrocarbon molecules are discussed.

We present a novel method for the simulation of the vibration-induced autoionization dynamics in molecular anions in the framework of the quantum-classical surface hopping approach. Classical trajectories starting from quantum initial conditions are propagated on a quantum-mechanical potential energy surface while allowing for autoionization through transitions into discretized continuum states. These transitions are induced by the couplings between the electronic states of the bound anionic system and the electron-detached system composed of the neutral molecule and the free electron.A discretization scheme for the detached system is introduced and a set of formulae is derived which enables the approximate calculation of couplings between the bound and free-electron states.We demonstrate our method on the example of the anion of vinylidene, a high-energy isomer of acetylene, for which detailed experimental data is available. Our results provide information on the time scale of the autoionization process and give an insight into the energetic and angular distribution of the ejected electrons as well as into the associated changes of the molecular geometry. We identify the formation of structures with reduced C-C bond lengths and T-like conformations through bending of the CH2 group with respect to the C-C axis and point out the role of autoionization as a driving process for the isomerization to acetylene.

We report infrared spectra of xylylene isomers in the gas phase, using free electron laser (FEL) radiation. All xylylenes were generated by flash pyrolysis. The IR spectra were obtained by monitoring the ion dip signal, using a IR/UV double resonance scheme. A gas phase IR spectrum of para‐xylylene  was recorded, whereas ortho‐ and meta‐xylylene were found to partially rearrange to benzocyclobutene and styrene. Computations of the UV oscillator strength  for all molecules were carried out and provde an explanation for the observation of the isomerization products.