Femtosecond real-time probing of reactions. 12. Vectorial dynamics of transition states

Femtosecond time-resolved techniques with KETOF (kinetic energy time-of-flight) detection in a molecular beam are developed for studies of the vectorial dynamics of transition states. Application to the dissociation reaction of IHgI is presented. For this system, the complex [I---Hg---I](++)* is unstable and, through the symmetric and asymmetric stretch motions, yields different product fragments: [I---Hg---I](++)* -> HgI(X^2/sigma^+) + I(^2P_3/2) [or I*(^2P_l/2)] (1a); [I---Hg---I](++)* -> Hg(^1S_0) + I(^2P_3/2) + I(^2P_3/2) [or I* (^2P_1/2)] (1 b). These two channels, (1a) and (1b), lead to different kinetic energy distributions in the products. It is shown that the motion of the wave packet in the transition-state region can be observed by MPI mass detection; the transient time ranges from 120 to 300 fs depending on the available energy. With polarized pulses, the vectorial properties (transition moments alignment relative to recoil direction) are studied for fragment separations on the femtosecond time scale. The results indicate the nature of the structure (symmetry properties) and the correlation to final products. For 311-nm excitation, no evidence of crossing between the I and I* potentials is found at the internuclear separations studied. (Results for 287-nm excitation are also presented.) Molecular dynamics simulations and studies by laser-induced fluorescence support these findings.

The English novel in the time of Shakespeare

The rise of the English novel needs rethinking after it has been confined to the "formal realism" of Defoe, Richardson, and Fielding (Watt, 1957), to "antecedents, forerunners" (Schlauch, 1968; Klein, 1970) or to mere "prose fiction" (McKillop, 1951; Davis, Richetti, 1969; Fish, 1971; Salzman, 1985; Kroll, 1998). My paper updates a book by Jusserand under the same title (1890) by proving that the social and moral history of the long prose genre admits no strict separation of "novel" and "romance", as both concepts are intertwined in most fiction (Cuddon, Preston, 1999; Mayer, 2000). The rise of the novel, seen in its European context, mainly in France and Spain (Kirsch, 1986), and equally in England, was due to the melting of the nobility and high bourgeoisie into a "meritocracy", or to its failure, to become the new bearer of the national culture, around 1600. (Brink, 1998). My paper will concentrate on Euphues (1578), a negative romance, Euphues and His England (1580), a novel of manners, both by Lyly; Arcadia (1590-93) by Sidney, a political roman à clef in the disguise of a Greek pastoral romance; The Unfortunate Traveller (1594) by Nashe, the first English picaresque novel, and on Jack of Newbury (1596-97) by Deloney, the first English bourgeois novel. My analysis of the central values in these novels will prove a transition from the aristocratic cardinal virtues of WISDOM, JUSTICE, COURAGE, and HONOUR to the bourgeois values of CLEVERNESS, FAIR PLAY, INDUSTRY, and VIRGINITY. A similar change took place from the Christian virtues of LOVE, FAITH, HOPE to business values like SERVICE, TRUST, and OPTIMISM. Thus, the legacy of history proves that the main concepts of the novel of manners, of political romance, of picaresque and middle-class fiction were all developed in the time of Shakespeare.

Equilibrium K-shell excitation of highly ionized neon

Augerelectron emission from foil-excited Ne-ions (6 to 10 MeV beam energy) has been measured. The beam-foil time-of-flight technique has been applied to study electronic transitions of metastable states (delayed spectra) and to determine their lifetimes. To achieve a line identification for the complex structure observed in the prompt spectrum, the spectrum is separated into its isoelectronic parts by an Augerelectron-ion coincidence correlating the emitted electrons and the emitting projectiles of well defined final charge states q_f. Well resolved spectra were obtained and the lines could be identified using intermediate coupling Dirac-Fock multiconfiguration calculations. From the total KLL-Augerelectron transition probabilities observed in the electronion coincidence experiment for Ne (10 MeV) the amount of projectiles with one K-hole just behind a C-target can be estimated. For foil-excited Ne-projectiles in contrast to single collision results the comparison of transition intensities for individual lines with calculated transition probabilities yields a statistical population of Li- and Be-like configurations.

Femtosecond spectroscopy of molecular autoionization and fragmentation

Femtosecond laser pulses are applied to the study of the dynamics and the pathways of multiphoton-induced ionization, autoionization, and fragmentation of Na_2 in molecular-beam experiments. In particular, we report on first results obtained studying electronic autoionization (leading to Na_2{^+} + {e ^-}) and autoionization-induced fragmentation (leading to Na{^+} + Na + {e ^-}) of a bound doubly excited molecular state. The final continuum states are analyzed by photoelectron spectroscopy and by measuring the mass and the released kinetic energy of the corresponding ionic fragments with a time-of-flight arrangement.

Femtosecond time-resolved molecular multiphoton ionization: the Na_2 system

We report here the first experimental study of femtosecond time-resolved molecular multiphoton ionization. Femtosecond pump-probe techniques are combined with time-of-flight spectroscopy to measure transient ionization spectra of Na_2 in a molecular-beam experiment. The wave-packet motions in different molecular potentials show that incoherent contributions from direct photoionization of a singly excited state and from excitation and autoionization of a bound doubly excited molecular state determine the observed transient ionization signal.

Femtosecond two-photon ionization spectroscopy of the B state of Na_3 clusters

We report time-resolved experiments studying the dynamics of the Na_3 B-X system. Femtosecond pump-probe techniques combined with ion time-of-flight (TOF) and zero kinetic energy (ZEKE) photoelectron spectroscopy allow us to observe the three-dimensional wavepacket motion in the excited Na_3 B state and in the Na_3 X state. The ground state wavepacket is induced by stimulated emission pumping during the pump pulse. The X-state dynamics is dominated by the three vibrational modes of the Na_3. Furthermore we observed pseudorotational wavepacket motion in the B state. We do not observe a fragmentation of the B state within a time interval of 10 ps.