We review the theory of intense laser alignment of molecules and present a survey of the many recent developments in this rapidly evolving field. Starting with a qualitative discussion that emphasizes the physical mechanism responsible for laser alignment, we proceed with a detailed exposition of the underlying theory, focusing on aspects that have not been presented in the past. Application of the theory in several pedagogical illustrations is then followed by a review of the recent experimental and theoretical advances in the field. We conclude with a discussion of new directions, future opportunities, and areas where we expect intense laser alignment to play a role in the future. Throughout we emphasize the recent evolution of the method of nonadiabatic alignment from isolated diatomic molecules to complex media.

Nonadiabatic Alignment by Intense Pulses. Concepts, Theory, and Directions

The angular momentum of molecules, or, equivalently, their rotation in three-dimensional space, is ideally suited for quantum control. Molecular angular momentum is naturally quantized, time evolution is governed by a well-known Hamiltonian with only a few accurately known parameters, and transitions between rotational levels can be driven by external fields from various parts of the electromagnetic spectrum. Control over the rotational motion can be exerted in one-, two-, and many-body scenarios, thereby allowing one to probe Anderson localization, target stereoselectivity of bimolecular reactions, or encode quantum information to name just a few examples. The corresponding approaches to quantum control are pursued within separate, and typically disjoint, subfields of physics, including ultrafast science, cold collisions, ultracold gases, quantum information science, and condensed-matter physics. It is the purpose of this review to present the various control phenomena, which all rely on the same underlying physics, within a unified framework. To this end, recall the Hamiltonian for free rotations, assuming the rigid rotor approximation to be valid, and summarize the different ways for a rotor to interact with external electromagnetic fields. These interactions can be exploited for control—from achieving alignment, orientation, or laser cooling in a one-body framework, steering bimolecular collisions, or realizing a quantum computer or quantum simulator in the many-body setting.

Quantum control of molecular rotation

This is a review of some recent development in femtosecond filamentation science with emphasis on our collective work. Previously reviewed work in the field will not be discussed. We thus start with a very brief description of the fundamental physics of single filamentation of powerful femtosecond laser pulses in air. Intensity clamping is emphasized. One consequence is that the peak intensity inside one or more filaments would not increase significantly even if one focuses the pulse at very high peak power even up to the peta-watt level. Another is that the clamped intensity is independent of pressure. One interesting outcome of the high intensity inside a filament is filament fusion which comes from the nonlinear change of index of refraction inside the filament leading to cross beam focusing. Because of the high intensity inside the filament, one can envisage nonlinear phenomena taking place inside a filament such as a new type of Raman red shift and the generation of very broad band supercontinuum into the infrared through four-wave-mixing. This is what we call by filamentation nonlinear optics. It includes also terahertz generation from inside the filament. The latter is discussed separately because of its special importance to those working in the field of safety and security in recent years. When the filamenting pulse is linearly polarized, the isotropic nature of air becomes birefringent both electronically (instantaneous) and through molecular wave packet rotation and revival (delayed). Such birefringence is discussed in detailed. Because, in principle, a filament can be projected to a long distance in air, applications to pollution measurement as well as other atmospheric science could be earned out. We call this filamentation atmospheric science. Thus, the following subjects are discussed briefly, namely, lightning control, rain making, remote measurement of electric field, microwave guidance and remote sensing of pollutants. A discussion on the higher order Kerr effect on the physics of filamentation is also given. This is a new hot subject of current debate. This review ends on giving our view of the prospect of progress of this field of filamentation in the future. We believe it hinges upon the development of the laser technology based upon the physical understanding of filamentation and on the reduction in price of the laser system.

Advances in intense femtosecond laser filamentation in air

We measure the instantaneous electronic nonlinear refractive index of N2, O2, and Ar at room temperature for a 90 fs and 800 nm laser pulse. Measurements are calibrated by post-pulse molecular alignment through a polarization technique. At low intensity, quadratic coefficients n2 are determined. At higher intensities, a strong negative contribution with a higher nonlinearity appears, which leads to an overall negative nonlinear Kerr refractive index in air above 26 TW/cm2.

https://hal.archives-ouvertes.fr/hal-00410677/document

Measurement of high order Kerr refractive index of major air components.

The goal of the present article is to review the major developments that have led to the current understanding of molecule-field interactions and experimental methods for manipulating molecules with electromagnetic fields. Molecule-field interactions are at the core of several, seemingly distinct, areas of molecular physics. This is reflected in the organization of this article, which includes sections on Field control of molecular beams, External field traps for cold molecules, Control of molecular orientation and molecular alignment, Manipulation of molecules by non-conservative forces, Ultracold molecules and ultracold chemistry, Controlled many-body phenomena, Entanglement of molecules and dipole arrays, and Stability of molecular systems in high-frequency super-intense laser fields. The article contains 853 references.

Manipulation of Molecules with Electromagnetic Fields

We report a direct nonintrusive observation of alignment and planar delocalization of ${\mathrm{C}\mathrm{O}}_{2}$ after an intense linearly polarized femtosecond laser pulse excitation. The effects are measured by a polarization technique involving a perturbative probe that itself does not induce appreciable alignment. We show that this technique allows one to measure a signal proportional to $⟨{cos﻿}^{2}\ensuremath{\theta}⟩\ensuremath{-}1/3$, with $\ensuremath{\theta}$ the angle between the molecular axis and the laser polarization. Simulations that support this analysis allow one to characterize the experimentally observed alignment and planar delocalization quantitatively.

Y. T. Pashayan

Papers

Postpulse molecular alignment measured by a weak field polarization technique.