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.

Femtosecond probing of sodium cluster ion Na_n ^+ fragmentation

We report on the first femtosecond time-resolved experiments in cluster physics. The photofragmentation dynamics of small sodium cluster ions Na_n ^+ have been studied with pump-probe techniques. Ultrashort laser pulses of 60-fs duration are employed to photoionize the sodium clusters and to probe the photofragments. We find that the ejection of neutral dimer Na_2 and, observed for the first time, neutral trimer Na_3 photofragments occur on ultrashort time scales of 2.5 and 0.4 ps, respectively. This and the absence of cluster heating reveals that direct photoinduced fragmentation processes are important at short times rather than the statistical unimolecular decay.

Femtosecond time-resolved wave packet motion in molecular multiphoton ionization and fragmentation

The dynamics of molecular multiphoton ionization and fragmentation of a diatomic molecule (Na_2) have been studied in molecular beam experiments. Femtosecond laser pulses from an amplified colliding-pulse mode-locked (CPM) ring dye laser are employed to induce and probe the molecular transitions. The final continuum states are analyzed by photoelectron spectroscopy, by ion mass spectrometry and by measuring the kinetic energy of the formed ionic fragments. Pump-probe spectra employing 70-fs laser pulses have been measured to study the time dependence of molecular multiphoton ionization and fragmentation. The oscillatory structure of the transient spectra showing the dynamics on the femtosecond time scale can best be understood in terms of the motion of wave packets in bound molecular potentials. The transient Na_2^+ ionization and the transient Na^+ fragmentation spectra show that contributions from direct photoionization of a singly excited electronic state and from excitation and autoionization of a bound doubly excited molecular state determine the time evolution of molecular multiphoton ionization.

Femtosecond dynamics of molecular and cluster ionization and fragmentation

The real-time dynamics of molecular (Na_2 . Na_3) and cluster Na_n (n=4-2l) multiphoton ionization and -fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Wave packet motion in the dimer Na_2 reveals two independent multiphoton ionization processes while the higher dimensional motion in the trimer Na_3 reflects the chaotic vibrational motion in this floppy system. The first studies of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na^*_n) ) with femtosecond laser pulses give a striking illustration of the transition from "molecule-like" excitations to "surfaceplasma"-like resonances for increasing cluster sizes. Time-resolved fragmentation of cluster ions Na_n^* indicate that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

High laser field effects in multiphoton ionization of Na_2

Femtosecond pump/probe multiphoton ionization experiments on Na_2 molecules are performed. The dependence of the total Na^+_2 ion signal on the delay time and the intensity of the femtosecond laser pulses is studied in detail. It is observed that molecular vibrational wavepacket motion in different electronic states dominates the time dependence of the ion signal. For higher laser intensities the relative contributions from the A ^1 \summe^+_u and the 2 ^1 \produkt__g states change dramatically, indicating the increasing importance of a two-electron versus a one-electron process. For even stronger fields (10 ^12 W/ cm²) a vibrational wavepacket in the electronic ground state X ^1 \summe^+_g is formed and its dynamics is also observed in the transient Na^+_2 signal. Time-dependent quantum calculations are presented. The theoretical results agree well with the experiment.

Femtosecond pump-probe study of the spreading and recurrence of a vibrational wave packet in Na_2

The motion of a vibrational wave packet in the bound A(^1 \summe^+_u) electronic state of the sodium dimer is detected in a femtosecond pump/probe molecular beam experiment. For short times harmonic motion is seen in the total ion yield of Na^+_2 as a function of delay time between the two laser pulses. The spreading of the wave packet results in the loss of the periodic variation of the ion signal. For longer delay times (47 ps) the wave packet regains its initial form which is reflected in the revival structure of the Na^+_2 signal. Time-dependent quantum calculations reproduce the measured effects.

Femtosecond time-resolved molecular multiphoton ionization and fragmentation of Na_2

We present a comparison between experimental and theoretical results for pump/probe multiphoton ionizing transitions of the sodium dimer, initiated by femtosecond laser pulses. It is shown that the motion of vibrational wavepackets in two electronic states is probed simultaneously and their dynamics is reflected in the total Na^+_2 ion signal which is recorded as a function of the time delay between pump and probe pulse. The time dependent quantum calculations demonstrate that two ionization pathways leading to the same final states of the molecularion exist: one gives an oscillating contribution to the ion signal, the other yields a constant background. From additional measurements of the Na^+ -transient photofragmentation spectrum it is deduced that another ionization process leading to different final ionic states exists. The process includes the excitation of a doubly excitedbound Rydberg state. This conclusion is supported by the theoretical simulation.

Femtosecond dynamics of molecules and clusters

The real-time dynamics of multiphoton ionization and fragmentation of molecules - Na_2 , Na_3 - and clusters - Na_n, Hg_n - has been studied in molecular beam experiments employing ion and electron spectroscopy together with femtosecond pump-probe techniques. Experiments with Na_2 and Na_3 reveal unexpected features of the dynamics of the absorption of several photons as seen in the one- and three dimensional vibrational wave packet motion in different potential surfaces and in high laser fields. Cluster size dependent studies of physical properties such as absorption resonances, lifetimes and decay channels have been performed using tunable femtosecond light pulses in resonance enhanced multiphoton ionization (REMPI) of the cluster size under investigation. This method failed in ns-laser experiments due to the ultrafast decay of the studied cluster. For Na_n, cluster we find that for cluster sizes n \le 21 molecular excitations and properties prevail over collective excitations of plasmon-like resonances. In the case of Hg_n cluster prompt formation of singly and doubly charged cluster are observed up to n \approx 60. The transient multiphoton ionization spectra show a 'short' time wave packet dynamics, which is identical for singly and doubly charged mercury clusters while the 'long' time fragmentation dynamics is different.

Electron-Nuclear Correlation in Laser-Driven Diatomic Molecules

The interaction of short intense laser pulses with atoms/molecules produces a multitude of highly nonlinear processes requiring a non-perturbative treatment. Detailed study of these highly nonlinear processes by numerically solving the time-dependent Schrodinger equation becomes a daunting task when the number of degrees of freedom is large. Also the coupling between the electronic and nuclear degrees of freedom further aggravates the computational problems. In the present work we show that the time-dependent Hartree (TDH) approximation, which neglects the correlation effects, gives unreliable description of the system dynamics both in the absence and presence of an external field. A theoretical framework is required that treats the electrons and nuclei on equal footing and fully quantum mechanically. To address this issue we discuss two approaches, namely the multicomponent density functional theory (MCDFT) and the multiconfiguration time-dependent Hartree (MCTDH) method, that go beyond the TDH approximation and describe the correlated electron-nuclear dynamics accurately. In the MCDFT framework, where the time-dependent electronic and nuclear densities are the basic variables, we discuss an algorithm to calculate the exact Kohn-Sham (KS) potentials for small model systems. By simulating the photodissociation process in a model hydrogen molecular ion, we show that the exact KS potentials contain all the many-body effects and give an insight into the system dynamics. In the MCTDH approach, the wave function is expanded as a sum of products of single-particle functions (SPFs). The MCTDH method is able to describe the electron-nuclear correlation effects as the SPFs and the expansion coefficients evolve in time and give an accurate description of the system dynamics. We show that the MCTDH method is suitable to study a variety of processes such as the fragmentation of molecules, high-order harmonic generation, the two-center interference effect, and the lochfrass effect. We discuss these phenomena in a model hydrogen molecular ion and a model hydrogen molecule. Inclusion of absorbing boundaries in the mean-field approximation and its consequences are discussed using the model hydrogen molecular ion. To this end, two types of calculations are considered: (i) a variational approach with a complex absorbing potential included in the full many-particle Hamiltonian and (ii) an approach in the spirit of time-dependent density functional theory (TDDFT), including complex absorbing potentials in the single-particle equations. It is elucidated that for small grids the TDDFT approach is superior to the variational approach.

Optimierung der laserinduzierten Plasmaspektroskopie an Metallen durch Femtosekunden-Doppelpulse für die Entwicklung eines hochauflösenden 3D-Rasterabbildungsverfahrens

Die laserinduzierte Plasmaspektroskopie (LIPS) ist eine spektrochemische Elementanalyse zur Bestimmung der atomaren Zusammensetzung einer beliebigen Probe. Für die Analyse ist keine spezielle Probenpräparation nötig und kann unter atmosphärischen Bedingungen an Proben in jedem Aggregatzustand durchgeführt werden. Femtosekunden Laserpulse bieten die Vorteile einer präzisen Ablation mit geringem thermischen Schaden sowie einer hohen Reproduzierbarkeit. Damit ist fs-LIPS ein vielversprechendes Werkzeug für die Mikroanalyse technischer Proben, insbesondere zur Untersuchung ihres Ermüdungsverhaltens. Dabei ist interessant, wie sich die initiierten Mikrorisse innerhalb der materialspezifschen Struktur ausbreiten. In der vorliegenden Arbeit sollte daher ein schnelles und einfach zu handhabendes 3D-Rasterabbildungsverfahren zur Untersuchung der Rissausbreitung in TiAl, einer neuen Legierungsklasse, entwickelt werden. Dazu wurde fs-LIPS (30 fs, 785 nm) mit einem modifizierten Mikroskopaufbau (Objektiv: 50x/NA 0.5) kombiniert, welcher eine präzise, automatisierte Probenpositionierung ermöglicht. Spektrochemische Sensitivität und räumliches Auflösungsvermögen wurden in energieabhängigen Einzel- und Multipulsexperimenten untersucht. 10 Laserpulse pro Position mit einer Pulsenergie von je 100 nJ führten in TiAl zum bestmöglichen Kompromiss aus hohem S/N-Verhältnis von 10:1 und kleinen Lochstrukturen mit inneren Durchmessern von 1.4 µm. Die für das Verfahren entscheidende laterale Auflösung, dem minimalen Lochabstand bei konstantem LIPS-Signal, beträgt mit den obigen Parametern 2 µm und ist die bislang höchste bekannte Auflösung einer auf fs-LIPS basierenden Mikro-/Mapping-Analyse im Fernfeld. Fs-LIPS Scans von Teststrukturen sowie Mikrorissen in TiAl demonstrieren eine spektrochemische Sensitivität von 3 %. Scans in Tiefenrichtung erzielen mit denselben Parametern eine axiale Auflösung von 1 µm. Um die spektrochemische Sensitivität von fs-LIPS zu erhöhen und ein besseres Verständnis für die physikalischen Prozesse während der Laserablation zu erhalten, wurde in Pump-Probe-Experimenten untersucht, in wieweit fs-Doppelpulse den laserinduzierten Abtrag sowie die Plasmaemission beeinflussen. Dazu wurden in einem Mach-Zehnder-Interferometer Pulsabstände von 100 fs bis 2 ns realisiert, Gesamtenergie und Intensitätsverhältnis beider Pulse variiert sowie der Einfluss der Materialparameter untersucht. Sowohl das LIPS-Signal als auch die Lochstrukturen zeigen eine Abhängigkeit von der Verzögerungszeit. Diese wurden in vier verschiedene Regimes eingeteilt und den physikalischen Prozessen während der Laserablation zugeordnet: Die Thermalisierung des Elektronensystems für Pulsabstände unter 1 ps, Schmelzprozesse zwischen 1 und 10 ps, der Beginn des Abtrags nach mehreren 10 ps und die Expansion der Plasmawolke nach über 100 ps. Dabei wird das LIPS-Signal effizient verstärkt und bei 800 ps maximal. Die Lochdurchmesser ändern sich als Funktion des Pulsabstands wenig im Vergleich zur Tiefe. Die gesamte Abtragsrate variiert um maximal 50 %, während sich das LIPS-Signal vervielfacht: Für Ti und TiAl typischerweise um das Dreifache, für Al um das 10-fache. Die gemessenen Transienten zeigen eine hohe Reproduzierbarkeit, jedoch kaum eine Energie- bzw. materialspezifische Abhängigkeit. Mit diesen Ergebnissen wurde eine gezielte Optimierung der DP-LIPS-Parameter an Al durchgeführt: Bei einem Pulsabstand von 800 ps und einer Gesamtenergie von 65 nJ (vierfach über der Ablationsschwelle) wurde eine 40-fache Signalerhöhung bei geringerem Rauschen erzielt. Die Lochdurchmesser vergrößerten sich dabei um 44 % auf (650±150) nm, die Lochtiefe um das Doppelte auf (100±15) nm. Damit war es möglich, die spektrochemische Sensitivität von fs-LIPS zu erhöhen und gleichzeitig die hohe räumliche Auflösung aufrecht zu erhalten.

Spatio-temporal resolution studies on a highly compact ultrafast electron diffractometer

Time-resolved diffraction with femtosecond electron pulses has become a promising technique to directly provide insights into photo induced primary dynamics at the atomic level in molecules and solids. Ultrashort pulse duration as well as extensive spatial coherence are desired, however, space charge effects complicate the bunching of multiple electrons in a single pulse.Weexperimentally investigate the interplay between spatial and temporal aspects of resolution limits in ultrafast electron diffraction (UED) on our highly compact transmission electron diffractometer. To that end, the initial source size and charge density of electron bunches are systematically manipulated and the resulting bunch properties at the sample position are fully characterized in terms of lateral coherence, temporal width and diffracted intensity.Weobtain a so far not reported measured overall temporal resolution of 130 fs (full width at half maximum) corresponding to 60 fs (root mean square) and transversal coherence lengths up to 20 nm. Instrumental impacts on the effective signal yield in diffraction and electron pulse brightness are discussed as well. The performance of our compactUEDsetup at selected electron pulse conditions is finally demonstrated in a time-resolved study of lattice heating in multilayer graphene after optical excitation.

Femtosecond wavepacket interferometry using the rotational dynamics of a trapped cold molecular ion

A Ramsey-type interferometer is suggested, employing a cold trapped ion and two time-delayed offresonant femtosecond laser pulses. The laser light couples to the molecular polarization anisotropy, inducing rotational wavepacket dynamics. An interferogram is obtained from the delay dependent populations of the final field-free rotational states. Current experimental capabilities for cooling and preparation of the initial state are found to yield an interferogram visibility of more than 80%. The interferograms can be used to determine the polarizability anisotropy with an accuracy of about ±2%, respectively ±5%, provided the uncertainty in the initial populations and measurement errors are confined to within the same limits.