Capturing electron-driven chiral dynamics in UV-excited molecules.

Chiral molecules, used in applications such as enantioselective photocatalysis, circularly polarized light detection and emission and molecular switches, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale and thereby control reactivity.

Photoelectron elliptical dichroism spectroscopy of resonance-enhanced multiphoton ionization the 3s, 3p and 3d Rydberg series in fenchone.

The resonance-enhanced multiphoton ionization of chiral molecules by elliptically polarized laser pulses produces photoelectron angular distributions that are forward/backward asymmetric with respect to the light propagation axis. We investigate this photoelectron elliptical dichroism in the (2 + 1)-photon ionization of fenchone molecules, using wavelength tunable femtosecond UV pulses. We show that the photoelectron elliptical asymmetry is extremely sensitive to the intermediate resonant states involved in the ionization process, and enables electronic couplings to be revealed that do not show up so clearly when using circularly polarized light.

Ultrafast relaxation investigated by photoelectron circular dichroism: an isomeric comparison of camphor and fenchone.

We study the isomeric effects using time resolved photoelectron circular dichroism (TR-PECD). Using a (1 + 1') pump-probe ionisation scheme with photoelectrons collected by the velocity map imaging technique, we compare the relaxation dynamics from the 3s-Rydberg state in 1,4-(+)-camphor with the one in its chiral isomer, 1,4-(-)-fenchone [Comby , 2016, , , 4514]. Our measurements revealed a similar lifetime for both isomers.

Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry.

Unravelling the main initial dynamics responsible for chiral recognition is a key step in the understanding of many biological processes. However, this challenging task requires a sensitive enantiospecific probe to investigate molecular dynamics on their natural femtosecond time scale. Here we show that, in the gas phase, the ultrafast relaxation dynamics of photoexcited chiral molecules can be tracked by recording time-resolved photoelectron circular dichroism (TR-PECD) resulting from the photoionization by a circularly polarized probe pulse.

Probing ultrafast dynamics of chiral molecules using time-resolved photoelectron circular dichroism.

Measuring the ultrafast dynamics of chiral molecules in the gas phase has been a long standing and challenging quest of molecular physics. The main limitation to reach that goal has been the lack of highly sensitive chiroptical measurement. By enabling chiral discrimination with up to several 10% of sensitivity, photoelectron circular dichroism (PECD) offers a solution to this issue.