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

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 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

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

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

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

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

Ultrafast nano-focusing with full optical waveform control

The spatial confinement and temporal control of an optical excitation on nanometer length scales and femtosecond time scales has been a long-standing challenge in optics. It would provide spectroscopic access to the elementary optical excitations in matter on their natural length and time scales and enable applications from ultrafast nano-opto-electronics to single molecule quantum coherent control. Previous approaches have largely focused on using surface plasmon polariton (SPP) resonant nanostructures or SPP waveguides to generate nanometer localized excitations. However, these implementations generally suffer from mode mismatch between the far-field propagating light and the near-field confinement. In addition, the spatial localization in itself may depend on the spectral phase and amplitude of the driving laser pulse thus limiting the degrees of freedom available to independently control the nano-optical waveform. Here we utilize femtosecond broadband SPP coupling, by laterally chirped fan gratings, onto the shaft of a monolithic noble metal tip, leading to adiabatic SPP compression and localization at the tip apex. In combination with spectral pulse shaping with feedback on the intrinsic nonlinear response of the tip apex, we demonstrate the continuous micro- to nano-scale self-similar mode matched transformation of the propagating femtosecond SPP field into a 20 nm spatially and 16 fs temporally confined light pulse at the tip apex. Furthermore, with the essentially wavelength and phase independent 3D focusing mechanism we show the generation of arbitrary optical waveforms nanofocused at the tip. This unique femtosecond nano-torch with high nano-scale power delivery in free space and full spectral and temporal control opens the door for the extension of the powerful nonlinear and ultrafast vibrational and electronic spectroscopies to the nanoscale.Comment: Contains manuscript with 4 figures as well as supplementary material with 2 figure

Coherent Control of Multiphoton Transitions with Femtosecond pulse shaping

We explore the effects of ultrafast shaped pulses for two-level systems that do not have a single photon resonance by developing a multiphoton density-matrix approach. We take advantage of the fact that the dynamics of the intermediate virtual states are absent within our laser pulse timescales. Under these conditions, the multiphoton results are similar to the single photon and that it is possible to extend the single photon coherent control ideas to develop multiphoton coherent control.Comment: 13 pages, 7 figures. submitted to PR

Shaping speckles: spatio-temporal focussing of an ultrafast pulse through a multiply scattering medium

The multiple scattering of coherent light is a problem of both fundamental and applied importance. In optics, phase conjugation allows spatial focussing and imaging through a multiply scattering medium; however, temporal control is nonetheless elusive, and multiple scattering remains a challenge for femtosecond science. Here, we report on the spatially and temporally resolved measurement of a speckle field produced by the propagation of an ultrafast optical pulse through a thick strongly scattering medium. Using spectral pulse shaping, we demonstrate the spatially localized temporal recompression of the output speckle to the Fourier-limit duration, offering an optical analogue to time-reversal experiments in the acoustic regime. This approach shows that a multiply scattering medium can be put to profit for light manipulation at the femtosecond scale, and has a diverse range of potential applications that includes quantum control, biological imaging and photonics.Comment: 7 pages, 3 figures, published in Nature Communication