RESUMO
Imaging in real time the complete dynamics of a process as fundamental as photoemission has long been out of reach because of the difficulty of combining attosecond temporal resolution with fine spectral and angular resolutions. Here, we achieve full decoding of the intricate angle-dependent dynamics of a photoemission process in helium, spectrally and anisotropically structured by two-photon transitions through intermediate bound states. Using spectrally and angularly resolved attosecond electron interferometry, we characterize the complex-valued transition probability amplitude toward the photoelectron quantum state. This allows reconstructing in space, time, and energy the complete formation of the photoionized wave packet.
RESUMO
The C4H4 isomer cyclobutadiene (CBD) is the prime model for antiaromaticity and thus a molecule of considerable interest in chemistry. Because it is highly reactive, it can only be studied under isolated conditions. Its electronic structure is characterized by a pseudo-Jahn-Teller effect in the neutral and a E â ß Jahn-Teller effect in the cation. As a result, recording photoelectron spectra as well as describing them theoretically has been challenging. Here we present the photoion mass-selected threshold photoelectron spectrum of cyclobutadiene together with a simulation based on time-dependent wavepacket dynamics that includes vibronic coupling in the ion, taking into account eight vibrational modes in the cation. Excellent agreement between theory and experiment is found, and the ionization energy is revised to 8.06 ± 0.02 eV.
RESUMO
Tolane (diphenylacetylene, C14H10) was studied by picosecond time-resolved photoionisation and photoelectron imaging in a supersonic jet. The low-energy part of the 1B1uâ S0 REMPI spectrum is very similar to an earlier LIF spectrum, however additional bands were observed at higher energies above the fluorescence cut-off. For a number of bands the dynamics were investigated via pump-probe photoionisation and photoelectron spectroscopy. Around the 1B1u origin the lifetimes are in the ns range, but they drop to some 10 ps at higher excitation energies. For the short-lived bands at higher energies a sequential two-step relaxation to a long-lived electronic state was observed proceeding via an intermediately populated state with a lifetime of 100-200 ps. By comparison with previous quantum chemical calculations we assign this state as the biradicalic trans-bent1Au state that is ionised in a two-photon process.