Fast fragmentation in core-excited molecules

Symmetry breaking is an important phenomenon connected to the excitation of core electrons in molecules. The fundamental question of whether inner-shell electronic-state orbitals are delocalized, and what the underlying mechanism for breaking the symmetry of a molecule upon dissociation are the subject of much debate, especially for the case of diatomic molecules. One method for studying molecular fragmentation, which is based upon a symmetry picture, is multicoincidence ion spectroscopy. Here we give a brief presentation of some of the applications of this technique, where symmetry, nuclear motion and the temporal signature are of importance.     

Quantum state tomography of dissociating molecules

Using tomographic reconstruction we determine the complete internuclear quantum state, represented by the Wigner function, of a dissociating I2 molecule based on femtosecond time resolved position and momentum distributions of the atomic fragments. The experimental data are recorded by timed ionization of the photofragments with an intense 20 fs laser pulse. Our reconstruction method, which relies on Jaynes's maximum entropy principle, will also be applicable to time resolved position or momentum data obtained with other experimental techniques.     

Dispersion-independent high-visibility quantum interference in ultrafast parametric down-conversion

We demonstrate the effective removal of intrinsic distinguishability between entangled-photon pairs in femtosecond spontaneous parametric down-conversion. High-visibility quantum interference is recovered (an increase to 96% from 17%) while preserving the high photon-flux density associated with the use of long nonlinear crystals. This new technique is expected to serve as a basic component in the preparation of multiphoton entangled states.     

Time-resolved studies of ultrafast wavepacket dynamics in hydrogen molecules

Recent advances in the study of quantum vibrations and rotations in the fundamental hydrogen molecules are reported. Using the deuterium molecules (D₂⁺ and D₂) as exemplars, the application of ultrafast femtosecond pump-probe experiments to study the creation and time-resolved imaging of coherent nuclear wavepackets is discussed. The ability to study the motion of these fundamental molecules in the time-domain is a notable milestone, made possible through the advent of ultrashort intense laser pulses with durations on sub-vibrational (and sub-rotational) timescales. Quantum wavepacket revivals are characterised for both vibrational and rotational degrees of freedom and quantum models are used to provide a detailed discussion of the underlying ultrafast physical dynamics for the specialist and non-specialist alike.     

Intramolecular electron scattering and electron transfer following autoionization in dissociating molecules

Resonant Auger decay of core-excited molecules during ultrafast dissociation leads to a Doppler shift of the emitted electrons depending on the direction of the electron emission relative to the dissociation axis. We have investigated this process by angle-resolved electron-fragment ion coincidence spectroscopy. Electron energy spectra for selected emission angles for the electron relative to the molecular axis reveal the occurrence of intermolecular electron scattering and electron transfer following the primary emission. These processes amount to approximately 25% of the resonant atomic Auger intensity emitted in the studied transition.     

Analysis and control of ultrafast photodissociation processes in organometallic molecules

In this paper we characterize the ultrafast fragmentation in electronically excited Fe(CO)₂(NO)₂ and CpMn(CO)₃ by means of femtosecond time-resolved spectroscopy combined with mass spectrometry. From the transient two-color multi-photon ionization data, it was possible to record the transients of the parent molecule ions and their photofragment ions. The experimentally observed decay times indicated an ultrafast loss of the first ligands (sub-100 fs decay times). Further we performed a feedback control experiment on the photofragmenting CpMn(CO)₃ molecular system in order to maximize the yield of desired ionic products through pulse modulation. The shape of the pulses obtained from optimization reflect well the intrinsic molecular dynamics during photofragmentation and the change of the CpMn(CO)⁺/CpMn(CO)₃ ⁺ ratio shows a clear evidence for the capability of the optimization method to find tailor-made system-specific pulses. Received 9 January 2001     

Multiple-beam interference patterns in optical fiber generated with ultrafast pulses and a phase mask

We compare the cladding patterns present in grating structures fabricated with an ultrafast laser and a phase mask with a cw beam interference model. We find that the observed patterns agree well with the model results for picosecond pulses; however, for femtosecond pulses, we show that the full bandwidth and the pulsed nature of the sources must be considered because the pattern can be affected by group-velocity walk-off. An interesting consequence of order walk-off is the possibility of pure two-beam interference generation with a phase mask in the femtosecond pulse regime.     

Strong optical fields induce ultrafast rearrangement of H-atoms in ethanol molecules

H-atoms in C₂H₅OH are rearranged by strong optical fields generated by intense, 100 fs long infrared laser pulses to form new bonds that lead to the H ₃ ⁺ molecular ion. This observation appears to be against the expectation that exposure of molecules to intensities of the order of 10¹⁵ W cm^?2 inevitably lead to multiple ionization of molecules followed by instantaneous Coulomb explosion into fragments. The polarization dependence of the H ₃ ⁺ signal and of the energy content of H ₃ ⁺ ions lead to believe that H-atom rear-rangement in ethanol occurs within a single 100 fs pulse.     

Vibrational relaxation of dye molecules investigated by ultrafast induced dichroism

Theoretical and experimental data are presented on the propagation of picosecond pulses in weakly excited dye solutions. It is shown that the so called coherence peak of the induced dichroism observed at short delay times depends on the vibronic relaxation and the excited state absorption of the dye molecules. Interpretation of the experimental results is considerably facilitated at low excitation level. The vibrational relaxation time in theS ₁ state of phenoxazone 9 was measured to be _v =0.8±0.3 ps, 0.7±0.2 ps and 0.7±0.2 ps, respectively, for the solvents dioxane, solid polystyrene and CCl₄. For rhodamine 6 G in ethanol we find _v =0.5±0.2 ps.     

Clocking ultrafast wave packet dynamics in molecules through UV-induced symmetry breaking

We investigate the use of UV-pump-UV-probe schemes to trace the evolution of nuclear wave packets in excited molecular states by analyzing the asymmetry of the electron angular distributions resulting from dissociative ionization. The asymmetry results from the coherent superposition of gerade and ungerade states of the remaining molecular ion in the region where the nuclear wave packet launched by the pump pulse in the neutral molecule is located. Hence, the variation of this asymmetry with the time delay between the pump and the probe pulses parallels that of the moving wave packet and, consequently, can be used to clock its field-free evolution. The performance of this method is illustrated for the H(2) molecule.     

Packing of molecules and hole formation in lyotropic systems

A vector field q (the order parameter of the molecular packing) describing the packing (specifically, the orientation) of membrane-forming amphiphilic molecules is introduced to describe the structures of lyotropic phases constructed from membranes. In the general case q·n≠0 (where n is the unit normal vector) and therefore the singularities of the vector field q are not determined uniquely by the topology of the surface. The condition q·n=0 signifies disruption of the packing of the molecules. This corresponds to holes, which can form in membranes when lyotropic systems are diluted. As an illustration, the simplest type of such singularities, in which the distribution of the field q around a hole is described by a part of an instanton with unit topological charge, is studied. It is shown that such a distribution guarantees the existence of a local minimum under the condition that the tension per unit length λ of the hole boundary is small compared with the deformation energy of the field q: λh/K≪l (K is the modulus of the orientational elasticity of the field q and h is the thickness of the membrane). The radius of the hole which is formed equals L≈2.52(K/λh)^1/3 and the energy E≈59.79K(λh/K)^1/3. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 8, 575–580 (25 October 1996)     

Local electronic structure and Fano interference in tunneling into a Kondo hole system

Motivated by the recent success of local electron tunneling into heavy-fermion materials, we study the local electronic structure around a single Kondo hole in an Anderson lattice model and the Fano interference pattern relevant to STM experiments. Within the Gutzwiller method, we find that an intragap bound state exists in the heavy Fermi liquid regime. The energy position of the intragap bound state is dependent on the on-site potential scattering strength in the conduction and f-orbital channels. Within the same method, we derive a new dI/dV formulation, which includes explicitly the renormalization effect due to the f-electron correlation. It is found that the Fano interference gives asymmetric coherent peaks separated by the hybridization gap. The intragap peak structure has a lorenzian shape, and the corresponding dI/dV intensity depends on the energy location of the bound state.     

Observation of molecules produced from a Bose-Einstein condensate

Molecules are created from a Bose-Einstein condensate of atomic 87Rb using a Feshbach resonance. A Stern-Gerlach field is applied, in order to spatially separate the molecules from the remaining atoms. For detection, the molecules are converted back into atoms, again using the Feshbach resonance. The measured position of the molecules yields their magnetic moment. This quantity strongly depends on the magnetic field, thus revealing an avoided crossing of two bound states at a field value slightly below the Feshbach resonance. This avoided crossing is exploited to trap the molecules in one dimension.