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

Intramolecular vibrational energy redistribution as state space diffusion: Classical-quantum correspondence

We study the intramolecular vibrational energy redistribution (IVR) dynamics of an effective spectroscopic Hamiltonian describing the four coupled high frequency modes of CDBrClF. The IVR dynamics ensuing from nearly isoenergetic zeroth-order states, an edge (overtone) and an interior (combination) state, is studied from a state space diffusion perspective. A wavelet based time-frequency analysis reveals an inhomogeneous phase space due to the trapping of classical trajectories. Consequently the interior state has a smaller effective IVR dimension as compared to the edge state.Comment: 5 pages, 3 figure

On Readout of Vibrational Qubits Using Quantum Beats

Readout of the final states of qubits is a crucial step towards implementing quantum computation in experiment. Although not scalable to large numbers of qubits per molecule, computational studies show that molecular vibrations could provide a significant (factor 2–5 in the literature) increase in the number of qubits compared to two-level systems. In this theoretical work, we explore the process of readout from vibrational qubits in thiophosgene molecule, SCCl2, using quantum beat oscillations. The quantum beats are measured by first exciting the superposition of the qubit-encoding vibrational states to the electronically excited readout state with variable time-delay pulses. The resulting oscillation of population of the readout state is then detected as a function of time delay. In principle, fitting the quantum beat signal by an analytical expression should allow extracting the values of probability amplitudes and the relative phases of the vibrational qubit states. However, we found that if this procedure is implemented using the standard analytic expression for quantum beats, a non-negligible phase error is obtained. We discuss the origin and properties of this phase error, and propose a new analytical expression to correct the phase error. The corrected expression fits the quantum beat signal very accurately, which may permit reading out the final state of vibrational qubits in experiments by combining the analytic fitting expression with numerical modelling of the readout process. The new expression is also useful as a simple model for fitting any quantum beat experiments where more accurate phase information is desired

Femtosecond probing of bimolecular reactions: The collision complex

Progress has been made in probing the femtosecond dynamics of transition states of chemical reactions.(1) The "half-collision" case of unimolecular reactions has been experimentally investigated for a number of systems and much theoretical work has already been developed.(2) For bimolecular reactions, the case of full collision, the zero of time is a problem which makes the femtosecond temporal resolution of the dynamics a difficult task

Femtosecond real-time probing of reactions. VIII. The bimolecular reaction Br+I2

In this paper, we discuss the experimental technique for real-time measurement of the lifetimes of the collision complex of bimolecular reactions. An application to the atom–molecule Br+I_2 reaction at two collision energies is made. Building on our earlier Communication [J. Chem. Phys. 95, 7763 (1991)], we report on the observed transients and lifetimes for the collision complex, the nature of the transition state, and the dynamics near threshold. Classical trajectory calculations provide a framework for deriving the global nature of the reactive potential energy surface, and for discussing the real-time, scattering, and asymptotic (product-state distribution) aspects of the dynamics. These experimental and theoretical results are compared with the extensive array of kinetic, crossed beam, and theoretical studies found in the literature for halogen radical–halogen molecule exchange reactions

Understanding highly excited states via parametric variations

Highly excited vibrational states of an isolated molecule encode the vibrational energy flow pathways in the molecule. Recent studies have had spectacular success in understanding the nature of the excited states mainly due to the extensive studies of the classical phase space structures and their bifurcations. Such detailed classical-quantum correspondence studies are presently limited to two or quasi two dimensional systems. One of the main reasons for such a constraint has to do with the problem of visualization of relevant objects like surface of sections and Wigner or Husimi distributions associated with an eigenstate. This neccesiates various alternative techniques which are more algebraic than geometric in nature. In this work we introduce one such method based on parametric variation of the eigenvalues of a Hamiltonian. It is shown that the level velocities are correlated with the phase space nature of the corresponding eigenstates. A semiclassical expression for the level velocities of a single resonance Hamiltonian is derived which provides theoretical support for the correlation. We use the level velocities to dynamically assign the highly excited states of a model spectroscopic Hamiltonian in the mixed phase space regime. The effect of bifurcations on the level velocities is briefly discussed using a recently proposed spectroscopic Hamiltonian for the HCP molecule.Comment: 12 pages, 9 figures, submitted to J. Chem. Phy

Femtosecond real-time probing of reactions. V. The reaction of IHgI

The dissociation reaction of HgI2 is examined experimentally using femtosecond transition-state spectroscopy (FTS). The reaction involves symmetric and antisymmetric coordinates and the transition-state is well-defined: IHgI*-->[IHgI][double-dagger]@B|Q[sub S[script ']]Q[sub a[script ']]q-->HgI+I. FTS is developed for this class of ABA-type reactions and recurrences are observed for the vibrating fragments (symmetric coordinate) along the reaction coordinate (antisymmetric coordinate). The translational motion is also observed as a "delay time" of the free fragments. Analysis of our FTS results indicates that the reaction wave packet proceeds through two pathways, yielding either I(2P3/2) or I*(2P1/2) as one of the final products. Dissociation into these two pathways leads to HgI fragments with different vibrational energy, resulting in distinct trajectories. Hence, oscillatory behaviors of different periods in the FTS transients are observed depending on the channel probed (~300 fs to ~1 ps). These results are analyzed using the standard FTS description, and by classical trajectory calculations performed on model potentials which include the two degrees of freedom of the reaction. Quantum calculations of the expected fluorescence of the fragment are also performed and are in excellent agreement with experiments

Analyzing intramolecular vibrational energy redistribution via the overlap intensity-level velocity correlator

Numerous experimental and theoretical studies have established that intramolecular vibrational energy redistribution (IVR) in isolated molecules has a heirarchical tier structure. The tier structure implies strong correlations between the energy level motions of a quantum system and its intensity-weighted spectrum. A measure, which explicitly accounts for this correaltion, was first introduced by one of us as a sensitive probe of phase space localization. It correlates eigenlevel velocities with the overlap intensities between the eigenstates and some localized state of interest. A semiclassical theory for the correlation is developed for systems that are classically integrable and complements earlier work focusing exclusively on the chaotic case. Application to a model two dimensional effective spectroscopic Hamiltonian shows that the correlation measure can provide information about the terms in the molecular Hamiltonian which play an important role in an energy range of interest and the character of the dynamics. Moreover, the correlation function is capable of highlighting relevant phase space structures including the local resonance features associated with a specific bright state. In addition to being ideally suited for multidimensional systems with a large density of states, the measure can also be used to gain insights into the phase space transport and localization. It is argued that the overlap intensity-level velocity correlation function provides a novel way of studying vibrational energy redistribution in isolated molecules. The correlation function is ideally suited to analyzing the parametric spectra of molecules in external fields.Comment: 16 pages, 13 figures (low resolution

Direct Imaging of Two-State Dynamics on the Amorphous Silicon Surface

Amorphous silicon is an important material, amidst a debate whether or not it is a glass. We produce amorphous Si surfaces by ion bombardment and vapor growth, and image discrete Si clusters which hop by two-state dynamics at 295 K. Independent of surface preparation, these clusters have an average diameter of ~5 atoms. Given prior results for metallic glasses, we suggest that this cluster size is a universal feature. The hopping activation free energy of 0.93 ± 0.15 eV is rather small, in agreement with a previously untested surface glass model. Hydrogenation quenches the two-state dynamics, apparently by increasing surface crystallinity