Femtochemistry: Atomic-Scale Dynamics of the Chemical Bond Using Ultrafast Lasers (Nobel Lecture) Copyright((c)) The Nobel Foundation 2000. We thank the Nobel Foundation, Stockholm, for permission to print this lecture.

Over many millennia, humankind has thought to explore phenomena on an ever shorter time scale. In this race against time, femtosecond resolution (1 fs=10(-15) s) is the ultimate achievement for studies of the fundamental dynamics of the chemical bond. Observation of the very act that brings about chemistry-the making and breaking of bonds on their actual time and length scales-is the wellspring of the field of femtochemistry, which is the study of molecular motions in the hitherto unobserved ephemeral transition states of physical, chemical, and biological changes. For molecular dynamics, achieving this atomic-scale resolution using ultrafast lasers as strobes is a triumph, just as X-ray and electron diffraction, and, more recently, STM and NMR spectroscopy, provided that resolution for static molecular structures. On the femtosecond time scale, matter wave packets (particle-type) can be created and their coherent evolution as a single-molecule trajectory can be observed. The field began with simple systems of a few atoms and has reached the realm of the very complex in isolated, mesoscopic, and condensed phases, as well as in biological systems such as proteins and DNA structures. It also offers new possibilities for the control of reactivity and for structural femtochemistry and femtobiology. This anthology gives an overview of the development of the field from a personal perspective, encompassing our research at Caltech and focusing on the evolution of techniques, concepts, and new discoveries.

Femtosecond Dynamics of Dioxygen - Picket-Fence Cobalt Porphyrins: Ultrafast Release of O(2) and the Nature of Dative Bonding.

The ultrafast release of O(2) from the O(2) adduct of picket-fence cobalt porphyrin (see picture) has been probed in real time, and has a total reaction time of 2 ps, without subsequent recombination over several nanoseconds. The dynamics of this ultrafast release of O(2) shows that relaxation within the porphyrin system (200 fs) precedes porphyrin-to-metal electron transfer, but the latter occurs at an enhanced rate (500 fs as opposed to the more usual 1 - 2 ps) because of the dative bonding of cobalt and O(2), which gives the adduct ground state significant Co(III)-O(2)(-) character.

Femtosecond Dynamics of Norrish Type-II Reactions: Nonconcerted Hydrogen-Transfer and Diradical Intermediacy.

Norrish type-II and McLafferty rearrangements, which both involve an intramolecular transfer of a gamma H atom, can be differentiated on the femtosecond time scale. The McLafferty rearrangement results in ion fragmentation of the parent ketone, whereas the Norrish type-II reaction leads to a diradical species, which then either cyclizes or fragments (see scheme). For Norrish type-II reactions, the reaction time for the transfer of the hydrogen atom is within 70 - 90 fs, and the lifetime of the diradical intermediate is in the range of 400 - 700 ps at the total energy studied.

Femtosecond activation of reactions and the concept of nonergodic molecules

The description of chemical reaction dynamics often assumes that vibrational modes are well coupled (ergodic) and redistribute energy rapidly with respect to the course of the reaction. To experimentally probe nonergodic, nonstatistical behavior, studies of a series of reactions induced by femtosecond activation for molecules of varying size but having the same reaction coordinates [CH2 - (CH2)n-2 - C = Odagger --> products, with n = 4, 5, 6, and 10] were performed. Comparison of the experimental results with theoretical electronic structure and rate calculations showed a two to four orders of magnitude difference, indicating that the basic assumption of statistical energy redistribution is invalid. These results suggest that chemical selectivity can be achieved with femtosecond activation even at very high energies.