We report on the first experimental demonstration of enantioselective rotational control of chiral molecules with a laser field. In our experiments, two enantiomers of propylene oxide are brought to accelerated unidirectional rotation by means of an optical centrifuge. Using Coulomb explosion imaging, we show that the centrifuged molecules acquire preferential orientation perpendicular to the plane of rotation, and that the direction of this orientation depends on the relative handedness of the enantiomer and the rotating centrifuge field. The observed effect is in agreement with theoretical predictions and is reproduced in numerical simulations of the centrifuge excitation followed by Coulomb explosion of the centrifuged molecules. The demonstrated technique opens new avenues in optical enantioselective control of chiral molecules with a plethora of potential applications in differentiation, separation and purification of chiral mixtures.

We explore a pure optical method for enantioselective orientation of chiral molecules by means of laser fields with twisted polarization. Several field implementations are considered, including a pair of delayed, cross-polarized laser pulses, an optical centrifuge, and polarization-shaped pulses. We show that these schemes lead to out-of-phase time-dependent dipole signals for different enantiomers, and we also predict a substantial permanent molecular orientation persisting long after the laser fields are over. The underlying classical orientation mechanism common to all of these fields is discussed, and its operation is demonstrated for a range of chiral molecules of various complexity: hydrogen thioperoxide (HSOH), propylene oxide (CHCHCHO), and ethyl oxirane (CHCHCHCHO). The presented results demonstrate generality, versatility, and robustness of this optical method for manipulating molecular enantiomers in the gas phase.

Orientation and alignment of molecules by ultrashort laser pulses is crucial for a variety of applications and has long been of interest in physics and chemistry, with the special emphasis on stereodynamics in chemical reactions and molecular orbitals imaging. As compared to the laser-induced molecular alignment, which has been extensively studied and demonstrated, achieving molecular orientation is a much more challenging task, especially in the case of asymmetric-top molecules. Here, we report the experimental demonstration of all-optical field-free three-dimensional orientation of asymmetric-top molecules by means of phase-locked cross-polarized two-color laser pulse. This approach is based on nonlinear optical mixing process caused by the off-diagonal elements of the molecular hyperpolarizability tensor. It is demonstrated on SO2 molecules and is applicable to a variety of complex nonlinear molecules.

We show, both classically and quantum mechanically, enantioselective orientation of gas phase chiral molecules excited by laser fields with twisted polarization. Counterintuitively, the induced orientation, whose direction is laser controllable, does not disappear after the excitation, but stays approximately constant long after the end of the laser pulses, behavior unique to chiral systems. We computationally demonstrate this long-lasting orientation using propylene oxide molecules (CH3CHCH2O, or PPO) as an example, and consider two kinds of fields with twisted polarization: a pair of delayed cross-polarized pulses, and an optical centrifuge. This novel chiral effect opens new avenues for detecting molecular chirality, measuring enantiomeric excess and separating enantiomers with the help of inhomogeneous external fields.

Molecular chirality is an omnipresent phenomenon of fundamental significance in physics, chemistry and biology. For this reason, search for novel techniques for enantioselective control, detection and separation of chiral molecules is of particular importance. It has been recently predicted that laser fields with twisted polarization may induce persistent enantioselective field-free orientation of chiral molecules. Here we report the first experimental observation of this phenomenon using propylene oxide molecules (CH 3 CHCH 2 O, or PPO) spun by an optical centrifuge -a laser pulse, whose linear polarization undergoes an accelerated rotation around its propagation direction. We show that PPO molecules remain oriented on a time scale exceeding the duration of the centrifuge pulse by several orders of magnitude. The demonstrated long-time field-free enantioselective orientation opens new avenues for optical manipulation, discrimination, and, potentially, separation of molecular enantiomers.