ABSTRACT
Atoms are usually thought of as achiral objects. However, one can construct superpositions of atomic states that are chiral [1]. Here, we show how to excite such superpositions with tailored light fields both in the weak-field and strong-field regimes, using realistic laser parameters. First, we use time-dependent Schrödinger equation simulations to demonstrate the creation of a time-dependent bound chiral wave packet in sodium atoms. Second, we show how the time-dependent handedness of this wave packet can be probed by photoelectron circular dichroism, in spite of the central symmetry of the core potential. Third, we use time-dependent Schrödinger equation simulations to show how chirality can be directly imprinted on a photoelectron wave packet created by strong-field ionization and introduce an unambiguous chiral measure that allows us to characterize its handedness.
ABSTRACT
Time-resolved valence photoelectron spectroscopy is an established tool for studies of ultrafast molecular dynamics in the gas phase. Here we demonstrate time-resolved XUV photoelectron spectroscopy from dilute aqueous solutions of organic molecules, paving the way to application of this method to photodynamics studies of organic molecules in natural environments, which so far have only been accessible to all-optical transient spectroscopies. We record static and time-resolved photoelectron spectra of a sample molecule, quinoline yellow WS, analyze its electronic structure, and follow the relaxation dynamics upon excitation with 400 nm pulses. The dynamics exhibit three time scales, of which a 250 ± 70 fs time scale is attributed to solvent rearrangement. The two longer time scales of 1.3 ± 0.4 and 90 ± 20 ps can be correlated to the recently proposed ultrafast excited-state intramolecular proton transfer in a closely related molecule, quinophthalone.
ABSTRACT
An autoionizing resonance in molecular N2 is excited by an ultrashort XUV pulse and probed by a subsequent weak IR pulse, which ionizes the contributing Rydberg states. Time- and angular-resolved photoelectron spectra recorded with a velocity map imaging spectrometer reveal two electronic contributions with different angular distributions. One of them has an exponential decay rate of 20 ± 5 fs, while the other one is shorter than 10 fs. This observation is interpreted as a manifestation of interference stabilization involving the two overlapping discrete Rydberg states. A formalism of interference stabilization for molecular ionization is developed and applied to describe the autoionizing resonance. The results of calculations suggest, that the effect of the interference stabilization is facilitated by rotationally-induced couplings of electronic states with different symmetry.
