Photodissociation, direct molecular dynamics

Photodissociation, direct molecular dynamics, nuclear motion Schrodinger equation, 365-373... 

Y. Kurosaki. Energy-flow dynamics in the molecular channel of propanal photodissociation, C2H5CHO -> C2H64-CO direct ab initio molecular dynamics study, J. Phys. Chem. A, 110 11230-11236(2006). 

Y. Kurosaki. Hydrogen-atom production channels of acetaldehyde photodissociation direct DFT molecular dynamics study, J. Mol. Struct. - THEOCHEM 850 9—16 (2008). 

Andresen, P. and Schinke, R. (1987). Dissociation of water in the first absorption band A model system for direct photodissociation, in Molecular Photodissociation Dynamics, ed. M.N.R. Ashfold and J.E. Baggott (Royal Society of Chemistry, London). 

Ab initio molecular dynamics studies of the photodissociation of formaldehyde, H2CO—>H2+C0 Direct classical trajectory calculations by MP2 and density functional theory""... 

In Chap. 3, wave packet propagation could be observed for nearly all of the alkali dimer and trimer systems considered, over a rather long time compared to the wave packet oscillation period. The wave packet dynamics - a fingerprint of the excited molecule - definitely characterize the excited bound electronic state of these molecules. However, with the results on K3 (excited with A 800 nm), another phenomenon, which often governs ultrafast molecular and cluster dynamics, comes into the discussion photodissociation induced by the absorption of single photons. This photoinduced dissociation permits detailed study of molecular dynamics such as breaking of bonds, internal energy transfer, and radiationless transitions. The availability of laser sources with pulses of a few tens of femtoseconds today opens a direct, i.e. real-time, view on this phenomenon. 

Detailed reaction dynamics not only require that reagents be simple but also that these remain isolated from random external perturbations. Theory can accommodate that condition easily. Experiments have used one of three strategies. (/) Molecules ia a gas at low pressure can be taken to be isolated for the short time between coUisions. Unimolecular reactions such as photodissociation or isomerization iaduced by photon absorption can sometimes be studied between coUisions. (2) Molecular beams can be produced so that motion is not random. Molecules have a nonzero velocity ia one direction and almost zero velocity ia perpendicular directions. Not only does this reduce coUisions, it also aUows bimolecular iateractions to be studied ia intersecting beams and iacreases the detail with which unimolecular processes that can be studied, because beams facUitate dozens of refined measurement techniques. (J) Means have been found to trap molecules, isolate them, and keep them motionless at a predetermined position ia space (11). Thus far, effort has been directed toward just manipulating the molecules, but the future is bright for exploiting the isolated molecules for kinetic and dynamic studies. 

Coherent anti-Stokes Raman scattering (CARS) spectra of O2 (15) and H2 (16) have been recently obtained. This opens up a very important class of molecules to direct detection. It is now possible, with the right parent molecule, to study the dynamics of the molecular detachment process. It will be particularly interesting to see the dynamical results that will be obtained in the future on the VUV photodissociation of hydrocarbons, such as the. vibrational and rotational excitation of the H2 product. 

The general theory for the absorption of light and its extension to photodissociation is outlined in Chapter 2. Chapters 3-5 summarize the basic theoretical tools, namely the time-independent and the time-dependent quantum mechanical theories as well as the classical trajectory picture of photodissociation. The two fundamental types of photofragmentation — direct and indirect photodissociation — will be elucidated in Chapters 6 and 7, and in Chapter 8 I will focus attention on some intermediate cases, which are neither truly direct nor indirect. Chapters 9-11 consider in detail the internal quantum state distributions of the fragment molecules which contain a wealth of information on the dissociation dynamics. Some related and more advanced topics such as the dissociation of van der Waals molecules, dissociation of vibrationally excited molecules, emission during dissociation, and nonadiabatic effects are discussed in Chapters 12-15. Finally, we consider briefly in Chapter 16 the most recent class of experiments, i.e., the photodissociation with laser pulses in the femtosecond range, which allows the study of the evolution of the molecular system in real time. 

In gas-phase dynamics, the discussion is focused on the TD quantum wave packet treatment for tetraatomic systems. This is further divided into two different but closed related areas molecular photofragmentation or half-collision dynamics and bimolecular reactive collision dynamics. Specific methods and examples for treating the dynamics of direct photodissociation of tetraatomic molecules and of vibrational predissociation of weakly bound dimers are given based on different dynamical characters of these two processes. TD methods such as the direct projection method for direct photodissociation, TD golden rule method and the flux method for predissociation are presented. For bimolecular reactive scattering, the use of nondirect product basis and the computation of the initial state-selected total reaction probabilities by flux calculation are discussed. The descriptions of these methods are supported by concrete numerical examples and results of their applications. 

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. 

The field of applications of molecular quantum dynamics covers broad areas of science not only in chemistry but also in physics and biology. Historically, due to the fact that the full quantum-mechanical simulation of molecular processes is limited to small systems, molecular quantum dynamics has given rise mainly to important applications of astrophysical and atmospheric relevance. In the interstellar medium or the Earth atmosphere, molecules are generally in the gas phase. Since many accurate spectroscopic data are available, these media have provided various prototype systems to study quantum effects in molecules and to calibrate the theoretical methods used to simulate these effects. In this context, it is not surprising that much theoretical effort is still directed toward modeling the full quantum-mechanical treatment of small molecules. Among others, one can cite the studies of the spectroscopy of water [159-161], and of the spectroscopy, photodissociation. 

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