Femtosecond Rotational Dynamics of D_{2} Molecules in Superfluid Helium Nanodroplets.

Rotational dynamics of D_{2} molecules inside helium nanodroplets is induced by a moderately intense femtosecond pump pulse and measured as a function of time by recording the yield of HeD^{+} ions, created through strong-field dissociative ionization with a delayed femtosecond probe pulse. The yield oscillates with a period of 185 fs, reflecting field-free rotational wave packet dynamics, and the oscillation persists for more than 500 periods. Within the experimental uncertainty, the rotational constant B_{He} of the in-droplet D_{2} molecule, determined by Fourier analysis, is the same as B_{gas} for an isolated D_{2} molecule. Our observations show that the D_{2} molecules inside helium nanodroplets essentially rotate as free D_{2} molecules.

Optimization of the double-laser-pulse scheme for enantioselective orientation of chiral molecules.

We present a comprehensive study of enantioselective orientation of chiral molecules excited by a pair of delayed cross-polarized femtosecond laser pulses. We show that by optimizing the pulses' parameters, a significant degree (∼10%) of enantioselective orientation can be achieved at 0 and 5 K rotational temperatures. This study suggests a set of reasonable experimental conditions for inducing and measuring strong enantioselective orientation. The strong enantioselective orientation and the wide availability of the femtosecond laser systems required for the proposed experiments may open new avenues for discriminating and separating molecular enantiomers.

Observation of Mechanical Faraday Effect in Gaseous Media.

We report the experimental observation of the rotation of the linear polarization of light propagating in a gas of fast-spinning molecules (molecular superrotors). In the observed effect, related to Fermi's prediction of "polarization drag" by a rotating medium, the vector of linear polarization tilts in the direction of molecular rotation. We use an optical centrifuge to bring the molecules in a gas sample to ultrafast unidirectional rotation and measure the polarization drag angles of the order of 10^{-4} rad (with an experimental uncertainty about 10^{-6} rad) over the propagation distance of the order of 1 mm in a number of gases under ambient conditions. We demonstrate an all-optical control of the drag magnitude and direction and investigate the robustness of the mechanical Faraday effect with respect to molecular collisions.

Long-Lasting Molecular Orientation Induced by a Single Terahertz Pulse.

We present a novel, previously unreported phenomenon appearing in a thermal gas of nonlinear polar molecules excited by a single THz pulse. We find that the induced orientation lasts long after the excitation pulse is over. In the case of symmetric-top molecules, the time-averaged orientation remains indefinitely constant, whereas in the case of asymmetric-top molecules the orientation persists for a long time after the end of the pulse. We discuss the underlying mechanism, study its nonmonotonous temperature and amplitude dependencies, and show that there exist optimal parameters for maximal residual orientation. The persistent orientation implies a long-lasting macroscopic dipole moment, which may be probed by even harmonic generation and may enable deflection by inhomogeneous electrostatic fields.

Controlled Enantioselective Orientation of Chiral Molecules with an Optical Centrifuge.

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.

Rotational Echoes as a Tool for Investigating Ultrafast Collisional Dynamics of Molecules.

We show that recently discovered rotational echoes of molecules provide an efficient tool for studying collisional molecular dynamics in high-pressure gases. Our study demonstrates that rotational echoes enable the observation of extremely fast collisional dissipation, at timescales of the order of a few picoseconds, and possibly shorter. The decay of the rotational alignment echoes in CO_{2} gas and CO_{2}-He mixture up to 50 bar was studied experimentally, delivering collision rates that are in good agreement with the theoretical expectations. The suggested measurement protocol may be used in other high-density media, and potentially in liquids.

All-optical field-free three-dimensional orientation of asymmetric-top molecules.

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.

Selective Orientation of Chiral Molecules by Laser Fields with Twisted Polarization.

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 (CH3CHCH2O), and ethyl oxirane (CH3CH2CHCH2O). The presented results demonstrate generality, versatility, and robustness of this optical method for manipulating molecular enantiomers in the gas phase.

Rotated echoes of molecular alignment: fractional, high order and imaginary.

We report experimental observations of rotated echoes of alignment induced by a pair of time-delayed and polarization-skewed femtosecond laser pulses interacting with an ensemble of molecular rotors. Rotated fractional echoes, rotated high order echoes and rotated imaginary echoes are directly visualized by using the technique of coincident Coulomb explosion imaging. We show that the echo phenomenon not only exhibits temporal recurrences but also spatial rotations determined by the polarization of the time-delayed second pulse. The dynamics of echo formation is well described by the laser-induced filamentation in rotational phase space. The quantum-mechanical simulation shows good agreements with the experimental results.

Dynamics and Hydrodynamics of Molecular Superrotors.

In recent years, several femtosecond laser techniques have been developed that can make gas molecules rotate extremely fast, whereas the gas stays translationally cold. Herein we use molecular-dynamics simulations to investigate the collisional dynamics of gases of such molecules ("superrotors"). We found that the common route of superrotors to equilibrium is rather generic. It starts with a long-lasting "gyroscopic stage", during which the molecules keep their fast rotation and the orientation of their angular momentum despite the many collisions they undergo. The inhibited rotational relaxation is characterized by a persistent anisotropy in the molecular angular distribution, manifested in long-lasting optical birefringence and in anisotropic diffusion of the gas. Later, the gyroscopic stage is abruptly terminated by a self-accelerating explosive rotational-translational energy exchange that generates sound and macroscopic vortices with a hot rotating core.

Exciting Molecules Close to the Rotational Quantum Resonance: Anderson Wall and Rotational Bloch Oscillations.

We describe a universal behavior of linear molecules excited by a periodic train of short laser pulses under conditions close to the quantum resonance. The quantum resonance effect causes an unlimited ballistic growth of the angular momentum. We show that a disturbance of the quantum resonance, either by the centrifugal distortion of the rotating molecules or a controlled detuning of the pulse train period from the so-called rotational revival time, eventually halts the growth by causing Anderson localization beyond a critical value of the angular momentum, the Anderson wall. Below the wall, the rotational excitation oscillates with the number of pulses due to a mechanism similar to Bloch oscillations in crystalline solids. We suggest optical experiments capable of observing the rotational Anderson wall and Bloch oscillations at near-ambient conditions with the help of existing laser technology.

Observation of Bloch Oscillations in Molecular Rotation.

We report the observation of rotational Bloch oscillations in a gas of nitrogen molecules kicked by a periodic train of femtosecond laser pulses. A controllable detuning from the quantum resonance creates an effective accelerating potential in angular momentum space, inducing Bloch-like oscillations of the rotational excitation. These oscillations are measured via the temporal modulation of the refractive index of the gas. Our results introduce room-temperature laser-kicked molecules as a new laboratory for studies of localization phenomena in quantum transport.

Collisional dynamics in a gas of molecular super-rotors.

Recently, femtosecond laser techniques have been developed that are capable of bringing gas molecules to extremely fast rotation in a very short time, while keeping their translational motion relatively slow. Here we study collisional equilibration dynamics of this new state of molecular gases. We show that the route to equilibrium starts with a metastable 'gyroscopic stage' in the course of which the molecules maintain their fast rotation and orientation of the angular momentum through many collisions. The inhibited rotational-translational relaxation is characterized by a persistent anisotropy in the molecular angular distribution, and is manifested in the optical birefringence and anisotropic diffusion in the gas. After a certain induction time, the 'gyroscopic stage' is abruptly terminated by an explosive rotational-translational energy exchange, leading the gas towards the final equilibrium. We illustrate our conclusions by direct molecular dynamics simulation of several gases of linear molecules.

Edge states of periodically kicked quantum rotors.

We present a quantum localization phenomenon that exists in periodically kicked three-dimensional rotors, but is absent in the commonly studied two-dimensional ones: edge localization. We show that under the condition of a fractional quantum resonance there are states of the kicked rotor that are strongly localized near the edge of the angular momentum space at J=0. These states are analogs of surface states in crystalline solids, and they significantly affect resonant excitation of molecular rotation by laser pulse trains.

Orientation and alignment echoes.

We present one of the simplest classical systems featuring the echo phenomenon-a collection of randomly oriented free rotors with dispersed rotational velocities. Following excitation by a pair of time-delayed impulsive kicks, the mean orientation or alignment of the ensemble exhibits multiple echoes and fractional echoes. We elucidate the mechanism of the echo formation by the kick-induced filamentation of phase space, and provide the first experimental demonstration of classical alignment echoes in a thermal gas of CO_{2} molecules excited by a pair of femtosecond laser pulses.

Anderson wall and BLOCH oscillations in molecular rotation.

We describe a universal behavior of linear molecules excited by a periodic train of short laser pulses under quantum resonance conditions. In a rigid rotor, the resonance causes an unlimited ballistic growth of the angular momentum. We show that the centrifugal distortion of rotating molecules eventually halts the growth, by causing Anderson localization beyond a critical value of the angular momentum--the Anderson wall. Its position solely depends on the molecular rotational constants and lies in the range of a few tens of ℏ. Below the wall, rotational excitation oscillates with the number of pulses due to a mechanism similar to Bloch oscillations in crystalline solids. We suggest optical experiments capable of observing the rotational Anderson wall and Bloch oscillations at near-ambient conditions with the help of existing laser technology.

Optics of a gas of coherently spinning molecules.

We consider the optical properties of a gas of molecules that are brought to fast unidirectional spinning by a pulsed laser field. It is shown that a circularly polarized probe light passing through the medium inverts its polarization handedness and experiences a frequency shift controllable by the sense and the rate of molecular rotation. Our analysis is supported by two recent experiments on the laser-induced rotational Doppler effect in molecular gases and provides a good qualitative and quantitative description of the experimental observations.

Laser-induced gas vortices.

Recently, several femtosecond-laser techniques have demonstrated molecular excitation to high rotational states with a preferred sense of rotation. We consider collisional relaxation in a dense gas of such unidirectionally rotating molecules, and suggest that due to angular momentum conservation, collisions lead to the generation of macroscopic vortex gas flows. This argument is supported using the Direct Simulation Monte Carlo method, followed by a computational gas-dynamic analysis.

Classical theory of rotational rainbow scattering from uncorrugated surfaces.

A classical perturbation theory is developed to study rotational rainbow scattering of molecules from uncorrugated frozen surfaces. Considering the interaction of the rigid rotor with the translational motion towards the surface to be weak allows for a perturbative treatment, in which the known zeroth order motion is that of a freely rotating molecule hitting a surface. Using perturbation theory leads to explicit expressions for the angular momentum deflection function with respect to the initial orientational angle of the rotor that are valid for any magnitude of the initial angular momentum. The rotational rainbows appear as peaks both in the final angular momentum and rotational energy distributions, as well as peaks in the angular distribution, although the surface is assumed to be uncorrugated. The derived analytic expressions are compared with numerical simulation data. Even when the rotational motion is significantly coupled to the translational motion, the predictions of the perturbative treatment remain qualitatively correct.

Cooling in a bistable optical cavity.

We propose a generic approach to nonresonant laser cooling of atoms and molecules in a bistable optical cavity. The method exemplifies a photonic version of Sisyphus cooling, in which the matter-dressed cavity extracts energy from the particles and discharges it to the external field as a result of sudden transitions between two stable states.