Spectroscopy aims at extracting information about matter through its interaction with light. However, when performed on gas and liquid phases as well as solid phases lacking long‐range order, the extracted spectroscopic features are in fact averaged over the molecular isotropic angular distributions. The reason is that light–matter processes depend on the angle between the transitional molecular dipole and the polarization of the light interacting with it. This understanding gave birth to the constantly expanding field of “laser‐induced molecular alignment”. In this paper, we attempt to guide the readers through our involvement (both experimental and theoretical) in this field in the last few years. We start with the basic phenomenon of molecular alignment induced by a single pulse, continue with selective alignment of close molecular species and unidirectional molecular rotation induced by two time‐delayed pulses, and lead up to novel schemes for manipulating the spatial distributions of molecular samples through rotationally controlled scattering off inhomogeneous fields and surfaces.

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.

We consider deflection of polarizable molecules by inhomogeneous optical fields, and analyze the role of molecular orientation and rotation in the scattering process. We show that by preshaping molecular angular distribution with the help of short and strong femtosecond laser pulses, one may efficiently control the scattering process, manipulate the average deflection angle and its distribution, and reduce substantially the angular dispersion of the deflected molecules. This opens new ways for many applications involving molecular focusing, guiding, and trapping by optical and static fields.

We study interaction of generic asymmetric molecules with laser fields having twisted polarization, using a pair of strong time-delayed short laser pulses with crossed linear polarizations as an example. We show that such an excitation not only provides unidirectional rotation of the most polarizable molecular axis, but also induces a directed torque along this axis, which results in a transient orientation of the molecules. The asymmetric molecules are chiral in nature and different molecular enantiomers experience the orienting action in opposite directions causing out-of-phase oscillations of their dipole moments. The resulting microwave radiation was recently suggested to be used for analysis or discrimination of chiral molecular mixtures. We reveal the mechanism behind this laser-induced orientation effect, show that it is classical in nature, and envision further applications of light with twisted polarization.

Mountain echoes are a well-known phenomenon, where an impulse excitation is mirrored by the rocks to generate a replica of the original stimulus, often with reverberating recurrences. For spin echoes in magnetic resonance and photon echoes in atomic and molecular systems the role of the mirror is played by a second, time delayed pulse which is able to reverse the flow of time and recreate the original event. Recently, laser-induced rotational alignment and orientation echoes were introduced for molecular gases, and discussed in terms of rotational-phase-space filamentation. Here we present, for the first time, a direct spatiotemporal analysis of various molecular alignment echoes by means of coincidence Coulomb explosion imaging. We observe hitherto unreported spatially rotated echoes, that depend on the polarization direction of the pump pulses, and find surprising imaginary echoes at negative times. PACS numbers:In 1950, Erwin Hahn reported [1] that if a spin system is irradiated by two properly timed and shaped pulses, a third pulse appears at twice the delay between the first two. The intuitive explanation was given in terms of time reversal, namely the second pulse reverses the direction of propagation of the original excitation, leading to reappearance of the original impulse [2]. In the absence of interaction with the environment, the full original excitation is recovered, but with environmental influences, various dephasing and energy loss processes may be probed. Following the original discovery in the realms of spins, echoes were observed in many other nonlinear physical situations such as photon echo [3], cyclotron echo [4], plasma wave echo [5], echoes in cold atoms [6,7], cavity QED [8], and even in particle accelerators [9,10]. Echoes form the basis for many modern methodologies ranging from Magnetic Resonance Imaging (MRI) [11] to short-wavelength radiation generation in free-electron * lasers [12][13][14][15]. Echoes are a classical phenomenon that is different from another well-known effect: quantum revivals [16][17][18] which are caused by the energy quantization of physical systems. Recently, a new type of echoes was introduced: molecular alignment echoes [19,20]. When a gas of molecules undergoes excitation by an ultrashort laser pulse, the molecules experience a torque causing transient alignment of the ensemble along the laser polarization axis (for a review of laser molecular alignment, see [21][22][23][24]). A pair of time-delayed laser pulses results in three alignment events: two of them immediately following each excitation, and a third one, an echo, that appears with a delay equal to that between the exciting pulses. This delay can be shorter than the rotational revival time, so that the echo provides access to rapidly dephasing molecular dynamics. The formation of these echoes is caused by the kick-induced filamentation of the rotational phase space [19], a phenomenon well known in the physics of particle accelerators [32]. Moreover, fractional echoes were predicted and observed in mo...