Extracting molecular Hamiltonian structure from time-dependent fluorescence intensity data

We propose a formalism for extracting molecular Hamiltonian structure from inversion of time-dependent fluorescence intensity data. The proposed method requires a minimum of \emph{a priori} knowledge about the system and allows for extracting a complete set of information about the Hamiltonian for a pair of molecular electronic surfaces.Comment: 7pages, no figures, LaTeX2

Coherent Optimal Control of Multiphoton Molecular Excitation

We give a framework for molecular multiphoton excitation process induced by an optimally designed electric field. The molecule is initially prepared in a coherent superposition state of two of its eigenfunctions. The relative phase of the two superposed eigenfunctions has been shown to control the optimally designed electric field which triggers the multiphoton excitation in the molecule. This brings forth flexibility in desiging the optimal field in the laboratory by suitably tuning the molecular phase and hence by choosing the most favorable interfering routes that the system follows to reach the target. We follow the quantum fluid dynamical formulation for desiging the electric field with application to HBr molecule.Comment: 5 figure

Transform-limited pulses are not optimal for resonant multiphoton transitions

Maximizing nonlinear light-matter interactions is a primary motive for compressing laser pulses to achieve ultrashort transform limited pulses. Here we show how, by appropriately shaping the pulses, resonant multiphoton transitions can be enhanced significantly beyond the level achieved by maximizing the pulse's peak intensity. We demonstrate the counterintuitive nature of this effect with an experiment in a resonant two-photon absorption, in which, by selectively removing certain spectral bands, the peak intensity of the pulse is reduced by a factor of 40, yet the absorption rate is doubled. Furthermore, by suitably designing the spectral phase of the pulse, we increase the absorption rate by a factor of 7.Comment: 4 pages, 3 figure

FAST CARS: Engineering a Laser Spectroscopic Technique for Rapid Identification of Bacterial Spores

Airborne contaminants, e.g., bacterial spores, are usually analyzed by time consuming microscopic, chemical and biological assays. Current research into real time laser spectroscopic detectors of such contaminants is based on e.g. resonant Raman spectroscopy. The present approach derives from recent experiments in which atoms and molecules are prepared by one (or more) coherent laser(s) and probed by another set of lasers. The connection with previous studies based on "Coherent Anti-Stokes Raman Spectroscopy" (CARS) is to be noted. However generating and utilizing maximally coherent oscillation in macromolecules having an enormous number of degrees of freedom is much more challenging. This extension of the CARS technique is called FAST CARS (Femtosecond Adaptive Spectroscopic Techniques for Coherent Anti-Stokes Raman Spectroscopy), and the present paper proposes and analyses ways in which it could be used to rapidly identify pre-selected molecules in real time.Comment: 43 pages, 21 figures; replacement with references added. Submitted to the Proceedings of National Academy of Science

Beable trajectories for revealing quantum control mechanisms

The dynamics induced while controlling quantum systems by optimally shaped laser pulses have often been difficult to understand in detail. A method is presented for quantifying the importance of specific sequences of quantum transitions involved in the control process. The method is based on a ``beable'' formulation of quantum mechanics due to John Bell that rigorously maps the quantum evolution onto an ensemble of stochastic trajectories over a classical state space. Detailed mechanism identification is illustrated with a model 7-level system. A general procedure is presented to extract mechanism information directly from closed-loop control experiments. Application to simulated experimental data for the model system proves robust with up to 25% noise.Comment: Latex, 20 pages, 13 figure

Optimal use of time dependent probability density data to extract potential energy surfaces

A novel algorithm was recently presented to utilize emerging time dependent probability density data to extract molecular potential energy surfaces. This paper builds on the previous work and seeks to enhance the capabilities of the extraction algorithm: An improved method of removing the generally ill-posed nature of the inverse problem is introduced via an extended Tikhonov regularization and methods for choosing the optimal regularization parameters are discussed. Several ways to incorporate multiple data sets are investigated, including the means to optimally combine data from many experiments exploring different portions of the potential. Results are presented on the stability of the inversion procedure, including the optimal combination scheme, under the influence of data noise. The method is applied to the simulated inversion of a double well system.Comment: 34 pages, 5 figures, LaTeX with REVTeX and Graphicx-Package; submitted to PhysRevA; several descriptions and explanations extended in Sec. I

Coherent control using adaptive learning algorithms

We have constructed an automated learning apparatus to control quantum systems. By directing intense shaped ultrafast laser pulses into a variety of samples and using a measurement of the system as a feedback signal, we are able to reshape the laser pulses to direct the system into a desired state. The feedback signal is the input to an adaptive learning algorithm. This algorithm programs a computer-controlled, acousto-optic modulator pulse shaper. The learning algorithm generates new shaped laser pulses based on the success of previous pulses in achieving a predetermined goal.Comment: 19 pages (including 14 figures), REVTeX 3.1, updated conten

Optimal Control of Molecular Motion Expressed Through Quantum Fluid Dynamics

A quantum fluid dynamic control formulation is presented for optimally manipulating atomic and molecular systems. In quantum fluid dynamic the control quantum system is expressed in terms of the probability density and the quantum current. This choice of variables is motivated by the generally expected slowly varying spatial-temporal dependence of the fluid dynamical variables. The quantum fluid dynamic approach is illustrated for manipulation of the ground electronic state dynamics of HCl induced by an external electric field.Comment: 18 pages, latex, 3 figure

Focusing and Compression of Ultrashort Pulses through Scattering Media

Light scattering in inhomogeneous media induces wavefront distortions which pose an inherent limitation in many optical applications. Examples range from microscopy and nanosurgery to astronomy. In recent years, ongoing efforts have made the correction of spatial distortions possible by wavefront shaping techniques. However, when ultrashort pulses are employed scattering induces temporal distortions which hinder their use in nonlinear processes such as in multiphoton microscopy and quantum control experiments. Here we show that correction of both spatial and temporal distortions can be attained by manipulating only the spatial degrees of freedom of the incident wavefront. Moreover, by optimizing a nonlinear signal the refocused pulse can be shorter than the input pulse. We demonstrate focusing of 100fs pulses through a 1mm thick brain tissue, and 1000-fold enhancement of a localized two-photon fluorescence signal. Our results open up new possibilities for optical manipulation and nonlinear imaging in scattering media

Reconstruction and control of a time-dependent two-electron wave packet

The concerted motion of two or more bound electrons governs atomic1 and molecular2,3 non-equilibrium processes including chemical reactions, and hence there is much interest in developing a detailed understanding of such electron dynamics in the quantum regime. However, there is no exact solution for the quantumthree-body problem, and as a result even the minimal system of two active electrons and a nucleus is analytically intractable4. This makes experimental measurements of the dynamics of two bound and correlated electrons, as found in the helium atom, an attractive prospect.However, although the motion of single active electrons and holes has been observed with attosecond time resolution5-7, comparable experiments on two-electron motion have so far remained out of reach. Here we showthat a correlated two-electron wave packet can be reconstructed froma 1.2-femtosecondquantumbeatamong low-lying doubly excited states in helium.The beat appears in attosecond transient-absorption spectra5,7-9 measured with unprecedentedly high spectral resolution and in the presence of an intensity-tunable visible laser field.Wetune the coupling10-12 between the two low-lying quantum states by adjusting the visible laser intensity, and use the Fano resonance as a phase-sensitive quantum interferometer13 to achieve coherent control of the two correlated electrons. Given the excellent agreement with large-scalequantum-mechanical calculations for thehelium atom, we anticipate thatmultidimensional spectroscopy experiments of the type we report here will provide benchmark data for testing fundamental few-body quantumdynamics theory in more complex systems. Theymight also provide a route to the site-specificmeasurement and control of metastable electronic transition states that are at the heart of fundamental chemical reactionsWe thank E. Lindroth for calculating the dipole moment (2p2|r|sp2,3+), and also A. Voitkiv, Z.-H. Loh, and R. Moshammer for helpful discussions. We acknowledge financial support by the Max-Planck Research Group Program of the Max-Planck Gesellschaft (MPG) and the European COST Action CM1204 XLIC. L. A. and F. M. acknowledge computer time from the CCC-UAM and Mare Nostrum supercomputer centers and financial support by the European Research Council under the ERC Advanced Grant no. 290853 XCHEM, the Ministerio de Economía y Competitividad projects FIS2010-15127, FIS2013-42002-R and ERA-Chemistry PIM2010EEC-00751, and the European grant MC-ITN CORIN