Femtosecond wave packet spectroscopy: Coherences, the potential, and structural determination

Recently, we presented a formalism for extracting highly resolved spectral information and the potential of bound isolated systems from coherent ultrafast laser experiments, using I2 as a model system [Gruebele et al., Chem. Phys. Lett. 166, 459 (1990)]. The key to this approach is the formation of coherent wave packets on the potential energy curve (or surface) of interest, and the measurement of their scalar and vector properties. Here we give a full account of the method by analyzing the coherences of the wave packet in the temporal transients of molecules excited by ultrashort laser pulses, either at room temperature, or in a molecular beam. From this, some general considerations for properly treating temporal data can be derived. We also present a direct inversion to the potential and quantum and classical calculations for comparison with the experiments

Optical analogs of NMR phase coherent multiple pulse spectroscopy

A new technique is presented for producing optical pulse sequences using acousto-optical modulation. The method is applied to gaseous I2 at −15 °C

Thermal Lensing Spectroscopy With Picosecond Pulse Trains and a New Dual Beam Configuration

In this communication, we wish to report on the use of synchronously mode-locked picosecond lasers in a pump-probe configuration for TL spectroscopy. The peak power for these picosecond lasers is very high and, of course, the fundamental of the dye laser (red beam) can be efficiently (~10%) doubled in frequency (U.V. beam) by second harmonic generation in nonlinear crystals. We use this generated U.V. beam as a probe to monitor the very weak absorption of the red beam. An arrangement [4] of the beams involving different waist positions for the pump and probe is used. This arrangement results in an enhancement of sensitivity (at least a factor of three to seven). Also, a different dependence of the signal on the cell position compared to the single beam method is obtained. Finally, we have obtained the Δν = 5 CH-stretching overtone absorption spectrum of liquid toluene with this method (see Figure 1). Suggestions are made regarding new applications of this picosecond pulse thermal lensing technique

Coherent photodissociation reactions: Observation by a novel picosecond polarization technique

In this communication, we wish to report on a novel picosecond polarization method for measuring the degree of rotational coherence that is preserved in photodissociation reactions. The systems studied here are jet-cooled van der Waals molecules; stilbene [4-6] bound [5] to He or Ne with a 1:1 composition.[7

Femtosecond real-time probing of reactions. XI. The elementary OClO fragmentation

Femtosecond reaction dynamics of OClO in a supersonic molecular beam are reported. The system is excited to the A 2A2 state with a femtosecond pulse, covering a range of excitation in the symmetric stretch between v1=17 to v1=11 (308–352 nm). A time-delayed femtosecond probe pulse ionizes the OClO, and OClO + is detected. This ion has not been observed in previous experiments because of its ultrafast fragmentation. Transients are reported for the mass of the parent OClO as well as the mass of the ClO. Apparent biexponential decays are observed and related to the fragmentation dynamics: OClO+hnu-->(OClO)[double-dagger]*-->ClO+O -->Cl+O2 . Clusters of OClO with water (OClO)n (H2O)m with n from 1 to 3 and m from 0 to 3 are also observed. The dynamics of the fragmentation reveal the nuclear motions and the electronic coupling between surfaces. The time scale for bond breakage is in the range of 300–500 fs, depending on v1; surface crossing to form new intermediates is a pathway for the two channels of fragmentation: ClO+O (primary) and Cl+O2 (minor). Comparisons with results of ab initio calculations are made

Four-dimensional ultrafast electron microscopy of phase transitions

Reported here is direct imaging (and diffraction) by using 4D ultrafast electron microscopy (UEM) with combined spatial and temporal resolutions. In the first phase of UEM, it was possible to obtain snapshot images by using timed, single-electron packets; each packet is free of space–charge effects. Here, we demonstrate the ability to obtain sequences of snapshots ("movies") with atomic-scale spatial resolution and ultrashort temporal resolution. Specifically, it is shown that ultrafast metal–insulator phase transitions can be studied with these achieved spatial and temporal resolutions. The diffraction (atomic scale) and images (nanometer scale) we obtained manifest the structural phase transition with its characteristic hysteresis, and the time scale involved (100 fs) is now studied by directly monitoring coordinates of the atoms themselves