Time-resolved excited state energetics of the solvated electron in sodium-doped water clusters.

The energetics and dynamics of the first electronically excited state of solvated electron in sodium-doped water clusters has been studied, by means of time-resolved electron spectra created in a pump-probe fs-laser experiment. The Na ··· (H2O)n clusters were excited by pulses at a wavelength of 795 nm, while ionization was achieved at a wavelength of 398 nm, and the overall cross-correlation fwhm was about 50 fs. Mass-resolved electron spectra were taken using photoelectron-photoion coincidence (PEPICO) spectroscopy for cluster sizes ranging from n = 1 up to 22. The electron spectra give new insights into the dynamics of the excited state of solvated electrons in Na ··· (H2O)n clusters. These dynamics are compared to known results for water cluster anions. In both cases, the observed dynamics are a combination of solvent rearrangement and internal energy conversion.

Ultrafast photo-excitation dynamics in isolated, neutral water clusters.

Using the efficient nonlinear conversion scheme which was recently developed in our group [M. Beutler, M. Ghotbi, F. Noack, and I. V. Hertel, Opt. Lett. 134, 1491 (2010); M. Ghotbi, M. Beutler, and F. Noack, ibid 35, 3492 (2010)] to provide intense sub-50 fs vacuum ultraviolet laser pulses we have performed the first real time study of ultrafast, photo-induced dynamics in the electronically excited Ã-state of water clusters (H(2)O)(n) and (D(2)O)(n) , n=2-10. Three relevant time scales, 1.8-2.5, 10-30, and 50-150 fs, can be distinguished which-guided by the available theoretical results-are attributed to H (D)-ejection, OH (OD) dissociation, and a nonadiabatic transition through a conical intersection, respectively. While a direct quantitative comparison is only very preliminary, the present results provide a crucial test for future modeling of excited state dynamics in water clusters, and should help to unravel some of the many still unresolved puzzles about water.

Single-pulse ultrafast laser imprinting of axial dot arrays in bulk glasses.

Ultrafast laser processing of bulk transparent materials can significantly gain flexibility when the number of machining spots is increased. We present a photoinscription regime in which an array of regular dots is generated before the region of main laser focus under single-pulse exposure in fused silica and borosilicate crown glass without any external spatial phase modulation. The specific position of the dots does not rely on nonlinear propagation effects but is mainly determined by beam truncation and is explained by a Fresnel propagation formalism taking into account beam apodization and linear wavefront distortions at the air/glass interface. The photoinscription regime is employed to generate a two-dimensional array of dots in fused silica. We show that an additional phase modulation renders flexible the pattern geometry.

Ultrafast dynamics in Na-doped water clusters and the solvated electron.

The lifetimes of the first electronically excited state of (H(2)O)(n)...Na and (D(2)O)(n)...Na clusters up to n = 40 have been measured by two-color pump-probe spectroscopy (800 and 400 nm) with 35 fs laser pulses. The excited-state lifetime decreases rapidly from 1.2 ps at n = 2 to approximately 100 fs at n > or = 10. For (D(2)O)(n)...Na, the average lifetime is about 3.6 times longer. The fast energy redistribution is explained by conversion of the electronic excitation into vibrations of the ground state. A simple model based on Fermi's Golden Rule predicts the observed trends but fails to reproduce the observed lifetimes quantitatively. The longer lifetimes for deuterated clusters are discussed in the framework of the famous energy gap law and indicate that the stretching modes of water play an important role in the energy-transfer process.

Dynamic ultrafast laser spatial tailoring for parallel micromachining of photonic devices in transparent materials.

Femtosecond laser processing of bulk transparent materials can generate localized positive changes of the refractive index. Thus, by translation of the laser spot, light-guiding structures are achievable in three dimensions. Increasing the number of laser processing spots can consequently reduce the machining effort. In this paper, we report on a procedure of dynamic ultrafast laser beam spatial tailoring for parallel photoinscription of photonic functions. Multispot operation is achieved by spatially modulating the wavefront of the beam with a time-evolutive periodical binary phase mask. The parallel longitudinal writing of multiple waveguides is demonstrated in fused silica. Using this technique, light dividers in three dimensions and wavelength-division demultiplexing (WDD) devices relying on evanescent wave coupling are demonstrated.

Fragmentation and ionization dynamics of C60 in elliptically polarized femtosecond laser fields.

Ionization and fragmentation of C60 fullerenes is studied in elliptically polarized, intense fs laser fields at 797 nm [I=(0.5-4.3)x10;{14} W cm;{-2}] and contrasted with Xe+, utilizing time-of-flight mass spectrometry. Very pronounced changes of parent and fragment ion yield as a function of ellipticity are observed. At lower intensities reduction of the ion yield for circular polarization establishes a coherent two-photon process connected with the key role of the LUMO+1(t_{1g}) "doorway state" and multielectron dynamics. Comparison with the behavior at 399 nm corroborates this finding. At high intensities enhanced fragmentation is observed which is tentatively attributed to returning loops of electron trajectories by the combined action of the C60+ field and the circular laser field.

Coherent control of bond breaking in amino acid complexes with tailored femtosecond pulses.

Intense femtosecond laser pulses, judiciously tailored in an adaptive, optimal control feedback loop were used to break preferentially the acyl-N ("peptide") bond of Ac-Phe-NHMe that may be regarded as a dipeptide model. We show that coherent excitation of complex wave packets in the strong-field regime allows to cleave strong backbone bonds in the molecular system preferentially, while keeping other more labile bonds intact. These results show the potential of pulse shaping as a powerful complementary analytical tool for protein sequencing of large biopolymers in addition to the well-known mass spectrometry and chemical analysis.

Control of giant breathing motion in c60 with temporally shaped laser pulses.

Femtosecond laser pulses tailored with closed-loop, optimal control feedback were used to excite oscillations in C60 with large amplitude by coherent heating of nuclear motion. A characteristic pulse sequence results in significant enhancement of C2 evaporation, a typical energy loss channel of vibrationally hot C60. The separation between subsequent pulses in combination with complementary two-color pump-probe data and time-dependent density functional theory calculations give direct information on the multielectron excitation via the t(1g) resonance followed by efficient coupling to the radial symmetric a(g)(1) breathing mode.

Ultrafast processes in OClO molecules excited by femtosecond laser pulses at 386-409 nm.

Ultrafast dissociation dynamics in OClO molecules is studied, induced by femtosecond laser pulses in the wavelength region from 386 to 409 nm, i.e., within the wide absorption band to the (approximately)A (2)A(2) electronic state. The decay of the initially excited state due to nonadiabatic coupling to the close lying (2)A(1) and (2)B(2) electronic states proceeds with a time constant increasing from 4.6 ps at 386 nm to 30 ps at 408.5 nm. Dissociation of the OClO molecule occurs after internal conversion within about 250 fs. In addition, a minor channel of direct excitation of the (2)A(1) electronic state has been identified, the lifetime of which increases from a few 100 fs at 386 nm to 2.2 ps at 408.5 nm. Simultaneous excitation of two neighboring vibrational bands in the (approximately)A (2)A(2) state leads to a coherent oscillation of the parent ion signal with the frequency difference of both modes.

Excited state dynamics and fragmentation channels of the protonated dipeptide H2N-Leu-Trp-COOH.

The excited state dynamics of the isolated and protonated peptide H(2)N-Leu-Trp-COOH are analyzed by fs pump-probe spectroscopy. The peptides are brought into the gas phase by electrospray ionization, and fs pump-probe excitation is detected by fragment ion formation. The pump laser addressed the excited pipi* state of the indole chromophore of the amino acid tryptophan. The subsequent excited state dynamics agreed with a biexponential decay with time constants of 500 fs and 10 ps. This is considerably shorter than the lifetime of neutral tryptophan in solution and in proteins, but similar to isolated, protonated tryptophan. Several models are discussed to explain the experimental results but the detailed quenching mechanism remains unresolved.

Relevance of pi sigma* states in the photoinduced processes of adenine, adenine dimer, and adenine-water complexes.

Ab initio calculations and time-resolved photoionization spectroscopy were carried out to characterize the role of the lowest two pi sigma* excited states for the photoinduced processes in the adenine monomer, adenine dimer, and adenine-water clusters. The calculations show--with respect to the monomer--a stabilization of 0.11-0.14 eV for the pi sigma* states in different isomers of adenine dimer and an even bigger stabilization of 0.14-0.36 eV for isomers of adenine-(H2O)1 and adenine-(H2O)3. Hence, the stabilized pi sigma* states should play an important role in the excited-state relaxation of partially or fully solvated adenine. This conclusion is supported by experimental results: In the adenine monomer, strong n pi* state signals are observed. Those signals are reduced in adenine dimer and vanish in water clusters due to the competing relaxation via the pi sigma* states.

Fragmentation dynamics of fullerenes in intense femtosecond-laser fields: loss of small neutral fragments on a picosecond time scale.

The fragmentation dynamics of C60 irradiated with intense femtosecond laser pulses is studied with one-color pump-probe spectroscopy. Small neutral fragments (C, C2, and C3) are formed by an 800-nm pump pulse which are then postionized by a delayed probe pulse. The respective ion signals detected by the time-of-flight mass spectrometry dramatically increase on a time scale of 10-20 ps.

Dynamics of photoinduced processes in adenine and thymine base pairs.

The excited-state dynamics of adenine and thymine dimers and the adenine-thymine base pair were investigated by femtosecond pump-probe ionization spectroscopy with excitation wavelengths of 250-272 nm. The base pairs showed a characteristic ultrafast decay of the initially excited pi pi* state to an n pi* state (lifetime tau(pi pi*) approximately 100 fs) followed by a slower decay of the latter with tau(n pi*) approximately 0.9 ps for (adenine)2, tau(n pi*) = 6-9 ps for (thymine)2, and tau(n pi*) approximately 2.4 ps for the adenine-thymine base pair. In the adenine dimer, a competing decay of the pi pi* state via the pi sigma* state greatly suppressed the n pi* state signals. Similarities of the excited-state decay parameters in the isolated bases and the base pairs suggest an intramonomer relaxation mechanism in the base pairs.

Photoelectron spectroscopy on thin films of extended zinc porphyrazines.

Photoemission measurements were performed on a series of stepwise benzoannelated zinc porphyrazine molecules in thin films. The electronic structure of tert-butyl-substituted zinc tetraazaporphyrin, phthalocyanine, and naphthalocyanine is investigated using mainly EUV synchrotron radiation. A detailed analysis of the zinc satellites in the spectra of the valence region is performed in an attempt to infer the effect of ligand size extension on the metal-ligand interactions. No differences in the character of the bond between zinc and ligand were detected as a function of ligand size. The results are compared with those for the respective metal-free and copper-containing molecules.

Ultrafast predissociation dynamics of water molecules excited to the electronic C and D states.

Two-photon excitation with femtosecond laser pulses in the spectral range 240-250 nm was used to prepare vapor phase H(2)O and D(2)O in the C (1)B(1) and D (1)A(1) states. Both states are predissociated via the B (1)A(1) state, forming excited OH/OD(A (2)Sigma(+)) as well as ground state OH/OD(X (2)Pi). We used ultrashort infrared probe pulses (1.65-2.42 microm) to control the ratio between these excited and ground state fragments originating from the dissociation process. Time resolved detection of the OH/OD(A (2)Sigma(+)) --> OH/OD(X (2)Pi) fluorescence allows us to monitor the dynamics of the predissociation. For the heterogeneous predissociation out of the C(1)B(1) state life times of (0.5 +/- 0.1) ps and (1.2 +/- 0.1) ps were found for H(2)O and D(2)O, respectively. The purely homogeneous character of the predissociation out of the D (1)A(1) state was monitored.

Theoretical study of the hydrogen atom transfer in the heterodimer indole-ammonia and comparison with experimental results.

Ab initio calculations on the heterodimer C8H6NH...NH3 are carried out for its ground, the excited pisigma*, and the ground cationic electronic states, enabling the description of hydrogen or proton transfer, respectively. Two-dimensional quantum-dynamical computations on the pisigma* potential surface help one to understand the mechanism and the time scale of the hydrogen transfer. Subsequent decay processes are discussed depending on the vibrational excitation of the ammonium constituent. Finally, the theoretical results obtained are used for the interpretation of the time-dependent signals observed in femtosecond pump-probe experiments.

Surface charging and impulsive ion ejection during ultrashort pulsed laser ablation.

We report time-resolved studies using femtosecond laser pulses, accompanied by model calculations, that illuminate the difference in the dynamics of ultrashort pulsed laser ablation of different materials. Dielectrics are strongly charged at the surface on the femtosecond time scale and undergo an impulsive Coulomb explosion. This is not seen from metals and semiconductors where the surface charge is effectively quenched.

Excitation of Rydberg series in C60.

Rydberg series of C60 are reported for the first time. The Rydberg states are seen in photoelectron spectra using ultrashort pulsed-laser excitation, where the excited states formed are ionized with one further photon from the same laser pulse. The structure is observed for pulse durations as short as 100 fs with indications of residual structure for even shorter pulse excitation. The production mechanism is discussed and the Rydberg states are modeled by analytically solving the Schrödinger equation with a simple jelliumlike potential for C60.

Generation of broadly tunable femtosecond vacuum-ultraviolet pulses.

Tunable femtosecond vacuum-ultraviolet radiation in the range omega(D) = 102-124 nm has been generated by twophoton-resonant and near-resonant four-wave difference-frequency mixing (omega(D) = 2omega(p) - omega(I)) in krypton and argon by use of intense 250-fs ArF laser pulses (omega(p)) and tunable femtosecond signal and idler pulses (omega(I)) generated by an optical parametric generator.