Nuclear motion spectroscopy

Although a separation of electronic and nuclear motion provides an important simplification and appealing qualitative model for chemistry, the electronic Sclirodinger equation is still fomiidable. Efforts to solve it approximately and apply these solutions to the study of spectroscopy, stmcture and chemical reactions fonn the subject of what is usually called electronic structure theory or quantum chemistry. The starting point for most calculations and the foundation of molecular orbital theory is the independent-particle approximation. 

Vos M H, Rappaport F, Lambry J-C, Breton J and Martin J-L 1993 Visualization of the coherent nuclear motion in a membrane protein by femtosecond spectroscopy Nature 363 320-5... 

The adiabatic picture developed above, based on the BO approximation, is basic to our understanding of much of chemistry and molecular physics. For example, in spectroscopy the adiabatic picture is one of well-defined spectral bands, one for each electronic state. The smicture of each band is then due to the shape of the molecule and the nuclear motions allowed by the potential surface. This is in general what is seen in absorption and photoelectron spectroscopy. There are, however, occasions when the picture breaks down, and non-adiabatic effects must be included to give a faithful description of a molecular system [160-163]. 

Infrared, Raman, microwave, and double resonance techniques turn out to offer nicely complementary tools, which usually can and have to be complemented by quantum chemical calculations. In both experiment and theory, progress over the last 10 years has been enormous. The relationship between theory and experiment is symbiotic, as the elementary systems represent benchmarks for rigorous quantum treatments of clear-cut observables. Even the simplest cases such as methanol dimer still present challenges, which can only be met by high-level electron correlation and nuclear motion approaches in many dimensions. On the experimental side, infrared spectroscopy is most powerful for the O—H stretching dynamics, whereas double resonance techniques offer selectivity and Raman scattering profits from other selection rules. A few challenges for accurate theoretical treatments in this field are listed in Table I. 

Coherent nuclear motion of reacting excited-state molecules in solution observed by ultrafast two color pump-probe spectroscopy... 

Unlike the case of simple diatomic molecules, the reaction coordinate in polyatomic molecules does not simply correspond to the change of a particular chemical bond. Therefore, it is not yet clear for polyatomic molecules how the observed wavepacket motion is related to the reaction coordinate. Study of such a coherent vibration in ultrafast reacting system is expected to give us a clue to reveal its significance in chemical reactions. In this study, we employed two-color pump-probe spectroscopy with ultrashort pulses in the 10-fs regime, and investigated the coherent nuclear motion of solution-phase molecules that undergo photodissociation and intramolecular proton transfer in the excited state. 

Vos, M. H., Rappaport, E., Lambry, J. C., Breton, J., and Martin, J. L., 1993, Visualization of coherent nuclear motion in a membrane protein by femtosecond spectroscopy. Nature,... 

Several recent reviews have presented broad overviews of ultrafast time-resolved spectroscopy [3-6], We shall concentrate instead on a selected, rather small subset of femtosecond time-resolved experiments carried out (and to a very limited extent, proposed) to date. In particular, we shall review experiments in which phase-coherent electronic or, more often, nuclear motion is induced and monitored with time resolution of less than 100 fs. The main reason for selectivity on this basis is the rather ubiquitous appearance of phase-coherent effects (especially vibrational phase coherence) in femtosecond spectroscopy. As will be discussed, nearly any spectroscopy experiment on molecular or condensed-phase systems is likely to involve phase-coherent vibrational motion if the time scale becomes short enough. Since the coherent spectral bandwidth of a femtosecond pulse often exceeds collective or molecular vibrational frequencies, such a pulse may perturb and be perturbed by a medium in a qualitatively different manner than a longer pulse of comparable peak power. The resulting spectroscopic possibilities are of special interest to these reviewers. 

It is important to realize that the only approximations that enter into this rate expression is the use of the Fenni golden-rule, which is compatible with the weak coupling nonadiabatic limit, and the Condon approximation which is known to be successful in applications to electronic spectroscopy. The solvent effect on the electronic process, including the slow dielectric response, must arise from the FC factor that contains contributions from all the surrounding intermolecular and intramolecular nuclear degrees of freedom. In fact, if the nuclear component of the solvent polarization was the only important nuclear motion in the system, then on the classical level of treatment used by Marcus Eqs (16.53) and (16.51) with Ea given by (16.49) should be equivalent. This implies that in this case... 

In Section 9.3 we have used this truncated dressed state picture to discuss photoabsorption and subsequent relaxation in a model described by a zero-order basis that includes the following states a molecular ground state with one photon of frequency doorway state with no-photons, l, 0), and a continuous manifold of states /) that drives the relaxation. This model is useful for atomic spectroscopy, however, in molecular spectroscopy applications it has to be generalized in an essential way—by accounting also for molecular nuclear motions. In the following section we make this generalization before turning to consider effects due to interaction with the thermal environment. 

Dynamics. Cluster dynamics constitutes a rich held, which focused on nuclear dynamics on the time scale of nuclear motion—for example, dissociahon dynamics [181], transihon state spectroscopy [177, 181, 182], and vibrahonal energy redistribuhon [182]. Recent developments pertained to cluster electron dynamics [183], which involved electron-hole coherence of Wannier excitons and exciton wavepacket dynamics in semiconductor clusters and quantum dots [183], ultrafast electron-surface scattering in metallic clusters [184], and the dissipahon of plasmons into compression nuclear modes in metal clusters [185]. Another interesting facet of electron dynamics focused on nanoplasma formation and response in extremely highly ionized molecular clusters coupled to an... 

INS spectroscopy avoids this problematic feedback effect, in the sense that it measures nuclear motion directly. This provides a simple relation between the amplitude of the motion, the cross section of the nuclei and the vibrational frequency to determine the intensity and shape of the spectral lines. The electron density is, of course, used to determine the potential energy surface that controls the nuclear motion but it is not involved in the calculation of the spectra. The combined use of INS spectroscopy, ab initio calculations and ACLIMAX can provide a good test of the molecular model, assessing the quality of structure and dynamics. 

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