Deuterium Isotope Effect on Internal Conversion of Ethylene Studied by Time-Resolved Photoelectron Spectroscopy.

The effect of deuterium isotopes on the internal conversion of ethylene is studied by using extreme ultraviolet time-resolved photoelectron spectroscopy. For deuterium-labeled ethylene, the time scale for ultrafast internal conversion is increased by a factor of approximately √2, in agreement with the results of ab initio multiple spawning calculations, indicating the essential role played by hydrogen motion in the conversion process. Following internal conversion, a metastable species with an electron binding energy of ∼9 eV is produced, and it decays with a time constant similar to that for both isotopologues.

Generation of sub-10-fs deep and extreme ultraviolet pulses for time-resolved photoemission spectroscopy.

We present a light source capable of generating sub-10-fs deep UV (DUV) and extreme UV (EUV) pulses for use in time-resolved photoemission spectroscopy. The fundamental output of a Ti:sapphire laser was compressed using the multi-plate method and mixed with the uncompressed second harmonic in a filamentation four-wave mixing process to generate sub-10-fs DUV pulses. Sub-10-fs EUV pulses were generated via high-order harmonic generation driven by the second harmonic pulses that were compressed using Ar gas and chirped mirrors. The minimum cross correlation time between 267 and 57 nm (corresponding to 21.7 eV) was measured to be 10.6 ± 0.4 fs.

Vibrational Motions in Ultrafast Electronic Relaxation of Pyrazine.

Ultrafast internal conversion via a conical intersection is ubiquitous in highly efficient photochemical reactions. Internal conversion from the 1ππ* to the 1nπ* state of pyrazine is the paradigm for this phenomenon; however, the relaxation occurs in such a short time (<20 fs) that the nuclear motion is difficult to observe in real time. The present study precisely measures the vibrational coherence transferred from the 1ππ* state to the 1nπ* state using time-resolved photoelectron spectroscopy with an unprecedented time resolution of 13.3 fs and reveals the key nuclear motions that drive the internal conversion.

Signatures of Conical Intersections in Extreme Ultraviolet Photoelectron Spectra of Furan Measured with 15 fs Time Resolution.

Ultrafast internal conversion of furan upon deep UV excitation at 200 nm is studied by using extreme ultraviolet time-resolved photoelectron spectroscopy with a time resolution of 15 fs. Ballistic nuclear wavepacket motion from the 1B2(ππ*) state to the ground state is fully observed using 21.7 eV probe pulses. Through the performance of a comparison with the results of electronic structure calculations at the MS(3)-CASPT2(10,10)/cc-pVTZ level of theory, the photoelectron signals from the conical intersection regions are identified.