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

Cascading is the process by which the exchange of energy between optical beams interacting via second order nonlinearities (χ(2)) leads to various effects such as nonlinear phase shifts, the generation of new beams, all-optical transistor action, the formation of soliton-like (solitary) waves, etc. Here we review the fundamentals of the processes and discuss experimental verification of the effects and various related applications.

χ(2) cascading phenomena and their applications to all-optical signal processing, mode-locking, pulse compression and solitons

By exploiting nonlinear optical effects, a technology of unprecedented flexibility for the production of tunable coherent light has been developed. Referred to as optical parametric generation, it provides sources with spectral coverage extending all the way from the ultraviolet to the mid-infrared, and with temporal coverage extending over all time domains from the femtosecond pulse to the continuous wave. Such sources generate coherent light of outstanding optical quality and are now finding wide-ranging applications.

https://science.sciencemag.org/content/sci/286/5444/1513.full.pdf

Parametric Generation of Tunable Light from Continuous-Wave to Femtosecond Pulses

Pulses with 180-THz bandwidth and 2?µJ energy were generated by a noncollinear optical parametric amplifier in the visible, pumped by the second harmonic of a Ti:sapphire laser. A portion of the amplified pulse spectrum was compressed to 7.2 fs by use of a thin prism sequence.

T.J. Driscoll

Papers

Ti:sapphire second-harmonic-pumped visible range femtosecond optical parametric oscillator

Generation of highly coherent tunable mid-infrared femtosecond pulses by paramatric frequency-mixing at 82 MHz