Summary form only given. Fundamental processes in atoms, molecules, as well as condensed matter are triggered or mediated by the motion of electrons inside or between atoms. Electronic dynamics on atomic length scales tends to unfold within tens to thousands of attoseconds (1 attosecond [as] = 10-18 s). Recent breakthroughs in laser science are now opening the door to watching and controlling these hitherto inaccessible microscopic dynamics. The key to accessing the attosecond time domain is the control of the electric field of (visible) light, which varies its strength and direction within less than a femtosecond (1 femtosecond = 1000 attoseconds). Atoms exposed to a few oscillations cycles of intense laser light are able to emit a single extreme ultraviolet (XUV) burst lasting less than one femtosecond. Full control of the evolution of the electromagnetic field in laser pulses comprising a few wave cycles have recently allowed the reproducible generation and measurement of isolated sub-femtosecond XUV pulses, demonstrating the control of microscopic processes (electron motion and photon emission) on an attosecond time scale. These tools have enabled us to visualize the oscillating electric field of visible light with an attosecond "oscilloscope", to control single-electron and probe multi-electron dynamics in atoms, molecules and solids. Recent experiments hold promise for the development of an attosecond X-ray source, which may pave the way towards 4D electron imaging with sub-atomic resolution in space and time.

Attosecond Physics

Over the last decade there have been spectacular developments in ultrafast laser technology, due to the introduction of solid state active materials and of new mode-locking and amplification techniques. These advances, together with the discovery of new nonlinear optical crystals, have fostered the introduction of ultrafast optical parametric amplifiers as a practical source of femtosecond pulses tunable across the visible and infrared spectral ranges. This article summarizes the recent progress in the development of ultrafast optical parametric amplifiers, giving the basic design principles for different frequency ranges and in addition presenting some advanced designs for the generation of ultrabroadband, few-optical-cycle pulses. Finally, we also briefly discuss the possibility of applying parametric amplification schemes to large-scale, petawatt-level systems.

Ultrafast optical parametric amplifiers

The primary photochemical event in vision, isomerization of the 11-cis chromophore in rhodopsin to the all-trans form, is one of the fastest natural photochemical processes known, taking less than a millionth of a millionth of a second. The molecular details of reactions of such rapidity are a stiff challenge to experimenters, but Polli et al. now report the characterization of the reaction using ultrafast optical spectroscopy with sub-20-femtosecond time resolution and spectral coverage from the visible to the near infrared. The data confirm that rhodopsin's extreme reactivity results from a molecular funnel mechanism that involves a 'conical intersection' between the potential energy surfaces of the starting and product molecules. Chemical reactions are usually described in terms of the movement of nuclei between the potential energy surfaces of ground and excited electronic states. Crossings known as conical intersections permit efficient transitions between the surfaces. It is shown here that ultrafast optical spectroscopy, with sub-20-fs time resolution and spectral coverage from the visible to the near-infrared, can map the isomerization of rhodopsin with sufficient resolution to shown that a conical intersection is important in this crucial event in vision. Ever since the conversion of the 11-cis retinal chromophore to its all-trans form in rhodopsin was identified as the primary photochemical event in vision1, experimentalists and theoreticians have tried to unravel the molecular details of this process. The high quantum yield of 0.65 (ref. 2), the production of the primary ground-state rhodopsin photoproduct within a mere 200 fs (refs 3–7), and the storage of considerable energy in the first stable bathorhodopsin intermediate8 all suggest an unusually fast and efficient photoactivated one-way reaction9. Rhodopsin's unique reactivity is generally attributed to a conical intersection between the potential energy surfaces of the ground and excited electronic states10,11 enabling the efficient and ultrafast conversion of photon energy into chemical energy12,13,14,15,16. But obtaining direct experimental evidence for the involvement of a conical intersection is challenging: the energy gap between the electronic states of the reacting molecule changes significantly over an ultrashort timescale, which calls for observational methods that combine high temporal resolution with a broad spectral observation window. Here we show that ultrafast optical spectroscopy with sub-20-fs time resolution and spectral coverage from the visible to the near-infrared allows us to follow the dynamics leading to the conical intersection in rhodopsin isomerization. We track coherent wave-packet motion from the photoexcited Franck–Condon region to the photoproduct by monitoring the loss of reactant emission and the subsequent appearance of photoproduct absorption, and find excellent agreement between the experimental observations and molecular dynamics calculations that involve a true electronic state crossing. Taken together, these findings constitute the most compelling evidence to date for the existence and importance of conical intersections in visual photochemistry.

Conical intersection dynamics of the primary photoisomerization event in vision

Coherent light sources have been widely used in control schemes that exploit quantum interference effects to direct the outcome of photochemical processes. The adaptive shaping of laser pulses is a particularly powerful tool in this context: experimental output as feedback in an iterative learning loop refines the applied laser field to render it best suited to constraints set by the experimenter. This approach has been experimentally implemented to control a variety of processes, but the extent to which coherent excitation can also be used to direct the dynamics of complex molecular systems in a condensed-phase environment remains unclear. Here we report feedback-optimized coherent control over the energy-flow pathways in the light-harvesting antenna complex LH2 from Rhodopseudomonas acidophila, a photosynthetic purple bacterium. We show that phases imprinted by the light field mediate the branching ratio of energy transfer between intra- and intermolecular channels in the complex's donor acceptor system. This result illustrates that molecular complexity need not prevent coherent control, which can thus be extended to probe and affect biological functions.

Quantum control of energy flow in light harvesting.

The development of femtosecond time-resolved methods for the study of gas-phase molecular dynamics is founded upon the seminal studies of Zewail and co-workers, as recognized in 1999 by the Nobel Prize in Chemistry.1 This methodology has been applied to chemical reactions ranging in complexity from bond-breaking in diatomic molecules to dynamics in larger organic and biological molecules, and has led to breakthroughs in our understanding of fundamental chemical processes. Photoexcited polyatomic molecules and anions often exhibit quite complex dynamics involving the redistribution of both charge and energy.2-6 These processes are the primary steps in the photochemistry of many polyatomic systems,7 are important in photobiological processes such as vision and photosynthesis,8 and underlie many concepts in molecular electronics.9 Femtosecond time-resolved methods involve a pump-probe configuration in which an ultrafast pump pulse initiates a reaction or, more generally, creates a nonstationary state or wave packet, the evolution of which is monitored as a function of time by means of a suitable probe pulse. Time-resolved or wave packet methods offer a view complementary to the usual spectroscopic approach and often yield a physically intuitive picture. Wave packets can behave as zeroth-order or even classical-like states and are therefore very helpful in discerning underlying dynamics. The information obtained from these experiments is very much dependent on the nature of the final state chosen in a given probe scheme. Transient absorption and nonlinear wave mixing are often the methods of choice in condensed-phase experiments because of their generality. In studies of molecules and clusters in the gas phase, the most popular methods, laser-induced fluorescence and resonant multiphoton ionization, usually require the probe laser to be resonant with an electronic transition in the species being monitored. However, as a chemical reaction initiated by the pump pulse evolves toward products, one expects that both the electronic and vibrational structures of the species under observation will change. Hence, these probe methods can be * To whom corresondence should be addressed. A.S.: telephone (613) 993-7388, fax (613) 991-3437, E-mail albert.stolow@nrc.ca. D.M.N.: telephone (510) 642-3505, fax (510) 642-3635, E-mail dan@radon.cchem.berkeley.edu. 1719 Chem. Rev. 2004, 104, 1719−1757

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Femtosecond time-resolved photoelectron spectroscopy.

Femtosecond pulses with center wavelengths between 470 and 750 nm are generated in a single-stage type I BBO optical parametric amplifier pumped by a frequency-doubled 1-kHz Ti:sapphire amplifier. A high-quality white-light continuum is used as the seed. Pulse durations as short as 16 fs and pulse energies of as much as 11 microJ are observed. The quantum efficiency is ~25% for both 7- and 40-microJ pump pulses. This unique combination of ultrashort pulse duration and high conversion is made possible by noncollinear phase matching that permits a sufficiently large amplification bandwidth. Simultaneously the group velocities of the signal and the idler are effectively matched. As a result widely tunable sub-20-fs pulses can be generated in a nonlinear crystal as thick as 2 mm.

Sub-20-fs pulses tunable across the visible from a blue-pumped single-pass noncollinear parametric converter.

Noncollinearly phase-matched optical parametric amplifiers (NOPAs) pumped by the blue light of a frequency-doubled Ti:sapphire regenerative amplifier are a convenient source of continuously tunable ultrashort pulses in the visible and near infrared for spectroscopic experiments. We present the underlying principles, report recent improvements and describe the experiences gained from the routine use of a number of NOPAs in our laboratories. We find that the setup can easily be optimized for the given experimental requirements. Typical output-pulse energies in the visible are 5 to 10 μJ and a few μJ in the NIR from 200 μJ regenerative-amplifier pulses at 800 nm. From 460 to 700 nm, pulse lengths between 10 and 20 fs are routinely achieved, while the length increases monotonically from about 20 fs at 900 nm to just below 50 fs at 1600 nm. In all cases this corresponds to a dramatic shortening compared to the length of the pump pulses of around 100 fs. First results show that the 700 to 900 nm region can be accessed with sub-50-fs pulse lengths by use of an intermediate white-light generator in a two-stage setup.

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Generation of 10 to 50 fs pulses tunable through all of the visible and the NIR

A two-stage blue-pumped noncollinearly phase matched optical parametric amplifier was used to generate near-infrared pulses that were continuously tunable from 865 to 1600 nm. The pulse lengths scaled from 20 fs at the shorter wavelengths to below 50 fs at 1600 nm, with a nearly Fourier-transform-limited bandwidth. From 200 µJ of 775-nm pump light at a 1-kHz repetition rate and a 130-fs duration, 7–2.5‐µJ pulse energies were generated, corresponding to a typical quantum efficiency of 25% from blue to near-infrared light.

20-50-fs pulses tunable across the near infrared from a blue-pumped noncollinear parametric amplifier.

Comprehensive measurement of the S1 azulene relaxation dynamics and observation of vibrational wavepacket motion

We demonstrate the operation of a 100 kHz noncollinear optical parametric amplifier that is pumped by just a few microjoules of 800 nm pulses with 50 fs duration. The device delivers sub-20 fs pulses tunable from 460 nm to beyond 1 μm and pulse energies up to 750 nJ when it is pumped with 7 μJ of energy. The design of the single-stage amplifier has been carefully optimized, and the design considerations are discussed.

J. Piel

Papers

Sub-20-fs pulses tunable across the visible from a blue-pumped single-pass noncollinear parametric converter.

Generation of 10 to 50 fs pulses tunable through all of the visible and the NIR

20-50-fs pulses tunable across the near infrared from a blue-pumped noncollinear parametric amplifier.

Comprehensive measurement of the S1 azulene relaxation dynamics and observation of vibrational wavepacket motion

Sub-20 fs visible pulses with 750 nJ energy from a 100 kHz noncollinear optical parametric amplifier