Femtosecond time scale reaction dynamics

Recently, Zewail and co-workers have combined the approaches of photodetachment and ultrafast spectroscopy to investigate the reaction dynamics of planar COT.iii They used a femtosecond photon pulse to carry out ionization of the COT ring-inversion transition state, generated by photodetachment as shown in Figure 5.4. From the photoionization efficiency, they were able to investigate the time-resolved dynamics of the transition state reaction, and observe the ring-inversion reaction of the planar COT to the tub-like D2d geometry on the femtosecond time scale. Thus, with the advent of new mass spectrometric techniques, it is now possible to examine detailed reaction dynamics in addition to traditional state properties." ... 

In addition to the natural improvements expected in the accuracy of the measurements, and the increased scope in the types of systems examined, new techniques go beyond the issue of thermochemistry to allow for very detailed studies of reaction dynamics. The investigation by Zewail and co-workers of the reactivity of planar COT" on the femtosecond time scale is likely only the beginning. Time-resolved photoelectron spectroscopy, for example, has recently been used to map the potential energy surfaces for the dissociation of simple ions IBr and l2. " Although applications in the field of organic reactive molecules are likely far off, they are now possible. 

In order to directly probe the dynamics of CT between Et and ZG, and to understand how the intervening DNA base stack regulates CT rate constants and efficiencies, we examined this reaction on the femtosecond time scale [96]. These investigations revealed not only the unique ability of the DNA n-stack to mediate CT, but also the remarkable capacity of dynamical motions to modulate CT efficiency. Ultrafast CT between tethered, intercalated Et and ZG was observed with two time constants, 5 and 75 ps, both of which were essentially independent of distance over the 10-17 A examined. Significantly, both time constants correspond to CT reactions, as these fast decay components were not detected in analogous duplexes where the ZG was re-... 

Norrish type-I reaction, has been studied over the years in extreme detail, with every imaginable physical and theoretical method at hand. Data gathered through studying such reactions on the femtosecond time scale, together with new theoretical work prompted by the dynamics observed, have provided a detailed picture of the processes involved and a fresh perspective on nonconcerted ot-cleavage events. 

I had the honor to review the field, as described by the title of this chapter. I would like to take this opportunity here to focus on some concepts that were essential in the development of femtochemistry reaction dynamics and control on the femtosecond time scale. The following is not an extensive review, as many books and articles have already been published [1-12] on the subject, but instead is a summary of our own involvement with the development of femtochemistry and the concept of coherence. Most of the original articles are given in a recent two-volume book that overviews the work at Caltech [5], up to 1994. 

Reaction dynamics on the femtosecond time scale are now studied in all phases of matter, including physical, chemical, and biological systems (see Fig. 1). Perhaps the most important concepts to have emerged from studies over the past 20 years are the five we summarize in Fig. 2. These concepts are fundamental to the elementary processes of chemistry—bond breaking and bond making—and are central to the nature of the dynamics of the chemical bond, specifically intramolecular vibrational-energy redistribution, reaction rates, and transition states. 

Third, it makes it possible to observe on a real-time basis the evolution of the most short-lived transient of reacting particles, that is, to study the molecular dynamics of chemical reactions in a femtosecond time scale [2]. Many papers presented at the XXth Solvay Conference were devoted to this possibility of implementing one-dimensional resolution along the reaction coordinate. The time resolution At corresponds to the spatial resolution Az At(v), where (v) is the average velocity along the reaction coordinate, for example, the velocity of the reaction products. At v) 3 x 104 cm/s, the quantity At - 100 fs corresponds to a one-dimensional (longitudinal) resolution of Az - 0.3 A. 

Techniques employing the ultraviolet (UV), visible, and near-infrared parts of the spectrum have the advantage of high sensitivity (single photon), high time resolution (femtoseconds), and moderate spatial resolution (on the order of 100 nm). Structural information is obtainable by infrared to radio-frequency techniques (e.g., magnetic resonance). Together, these techniques have enabled the visualization of individual molecules and the measurement of excited state dynamics from such molecules on the picosecond time scale. It is also possible to follow the time course of chemical reactions on the femtosecond time scale when... 

Recently, two basic questions of chemical dynamics have attracted much attention first, is it possible to detect ( film ) the nuclear dynamics directly on the femtosecond time scale and second, is it possible to direct (control) the nuclear dynamics directly as it unfolds These efforts of real-time detection and control of molecular dynamics are also known as femtosecond chemistry. Most of the work on the detection and control of chemical dynamics has focused on unimolecular reactions where the internuclear distances of the initial state are well defined within, of course, the quantum mechanical uncertainty of the initial vibrational state. The discussion in the following builds on Section 7.2.2, and we will in particular focus on the real-time control of chemical dynamics. It should be emphasized that the general concepts discussed in the present section are not limited to reactions in the gas phase. 

REACTION DYNAMICS ON THE FEMTOSECOND TIME SCALES 6.3.1. Ionization Mechanisms of Ammonia Clusters... 

More recently, the use of picosecond and femtosecond lasers in reaction dynamics opened up the field of femtochemistry, which was pioneered by Zewail [51-54]. The idea of these reactions is to photoinitiate the reactive process in a van der Waals complex. Sometimes, the process that is initiated is a simple dissociation or the isomerization of a free molecule. In each case, the reaction is initiated by a first ultrashort laser pulse (the pump pulse). It is analyzed after a certain delay by a second pulse (the probe pulse). This gives access to the reaction dynamics on the pertinent time-scale where chemical bonds are broken and others are formed. Depending on the system, this typically lasts between a few tenths of femtoseconds to hundredths of picoseconds. Recently the techniques of stereodynamies have been combined by Zewail and co-workers with femtosecond analysis [55, 56] to label specific reaction channels in electron-transfer reactions. 

Abstract A challenging task in surface science is to unravel the dynamics of molecules on surfaces associated with, for example, surface molecular motion and (bimolecular) reactions. As these processes typically take place on femtosecond time scales, ultrafast lasers must be used in these studies. We demonstrate two complementary approaches to study these ultrafast molecular dynamics at metal surfaces. In the first, the molecules are studied after desorbing from the surface initiated by a laser pulse using the so called time-of-flight technique. In the second approach, molecules are studied in real time during their diffusion over the surface by using surface-specific pump-probe spectroscopy. 

Lasers are the precision tools of photochemistry and they have been used to both pump (initiate) and probe (analyse) chemical processes on time-scales that are short enough to allow the direct observation of intramolecular motion and fragmentation (i.e. on the femtosecond time-scale). Thus, laser-based techniques provide us with one of the most direct and effective methods for investigating the mechanisms and dynamics of fundamental processes, such as photodissociation, photoionization and unimolecu-lar reactions. Avery wide variety of molecular systems have now been studied using laser techniques, and only a few selected examples can be described here. 

Another class of chemical reactions also covered here is that of proton-transfer reactions. These processes play a key role in solution chemistry, and more specifically in acid—base reactions. In this class of reactions the cmcial step involves the motion of the hydrogen atom, which typically occurs on the picosecond or femtosecond time-scale. By investigating the time dynamics of these processes in size-selected clusters, for a given system, information is gained at which specific cluster size the onset of the proton transfer reaction occurs. 

The chapters of this book are all theoretical in character. This reflects the fact that the conical intersection is a theoretical concept, and as such is not directly accessible to experimental observation. Nevertheless, the concepts, techniques and results discussed in this book are crucial for the interpretation of the observations in time-resolved spectroscopy and chemical kinetics on femtosecond time scales. It is hoped, therefore, that this book is of value not only for the theoretician, but also for the practitioneer in molecular spectroscopy, photochemistry, and collision-induced reaction dynamics. 

Su T, Chesnavich WJ. (1982) Parametrization of the ion-polar molecule collision rate-constant by trajectory calculations. J. Chem,. Phys. 76 5183-5185. Troe J, Lorquet JC, Manz J, Marcus RA, Herman M. (1997) Recent advances in statistical adiabatic channel calculations of state-specific dissociation dynamics. Chemical Reactions and Their Control on the Femtosecond Time Scale XXth Solvay Conference on Chemistry, Vol. 101, pp. 819-851. 

Femtosecond lasers represent the state-of-the-art in laser teclmology. These lasers can have pulse widths of the order of 100 fm s. This is the same time scale as many processes that occur on surfaces, such as desorption or diffusion. Thus, femtosecond lasers can be used to directly measure surface dynamics tlirough teclmiques such as two-photon photoemission [85]. Femtochemistry occurs when the laser imparts energy over an extremely short time period so as to directly induce a surface chemical reaction [86]. 

For very fast reactions, as they are accessible to investigation by pico- and femtosecond laser spectroscopy, the separation of time scales into slow motion along the reaction path and fast relaxation of other degrees of freedom in most cases is no longer possible and it is necessary to consider dynamical models, which are not the topic of this section. But often the temperature, solvent or pressure dependence of reaction rate... 

Under the simulation conditions, the HMX was found to exist in a highly reactive dense fluid. Important differences exist between the dense fluid (supercritical) phase and the solid phase, which is stable at standard conditions. One difference is that the dense fluid phase cannot accommodate long-lived voids, bubbles, or other static defects, whereas voids, bubbles, and defects are known to be important in initiating the chemistry of solid explosives.107 On the contrary, numerous fluctuations in the local environment occur within a time scale of tens of femtoseconds (fs) in the dense fluid phase. The fast reactivity of the dense fluid phase and the short spatial coherence length make it well suited for molecular dynamics study with a finite system for a limited period of time chemical reactions occurred within 50 fs under the simulation conditions. Stable molecular species such as H20, N2, C02, and CO were formed in less than 1 ps. 

Figure 9. Femtosecond dynamics of an elementary reaction (I2 — 21) in solvent (Ar) cages. The study was made in clusters for two types of excitation to the dissociative A state and to the predissociative B state. The potentials in the gas phase govern a much different time scale for bond breakage (femtosecond for A state and picosecond for B state). Based on the experimental transients, three snapshots of the dynamics are shown with the help of molecular dynamics simulations at the top. The bond breakage time, relative to solvent rearrangement, plays a crucial role in the subsequent recombination (caging) dynamics. Experimental transients for the A and B states and molecular dynamics simulations are shown.

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