Photoinitiated dynamics

C. Photoinitiated Dynamics of Higher Order Rg XY(X,v" = 0) Complexes Acknowledgments References... 

During the past decade, the study of photoinitiated reactive and inelastic processes within weakly bound gaseous complexes has evolved into an active area of research in the field of chemical physics. Such specialized microscopic environments offer a number of unique opportunities which enable scientists to examine regiospecific interactions at a level of detail and precision that invites rigorous comparisons between experiment and theory. Specifically, many issues that lie at the heart of physical chemistry, such as reaction probabilities, chemical branching ratios, rates and dynamics of elementary chemical processes, curve crossings, caging, recombination, vibrational redistribution and predissociation, etc., can be studied at the state-to-state level and in real time. 

Volk M, Kholodenko Y, Lu HSM, Gooding EA, DeGrado WF, Hochstrasser RM. Peptide conformational dynamics and vibrational Stark effects following photoinitiated disulfide cleavage. J Phys Chem B 1997 101 8607-8616. 

A study of chemically induced dynamic electron polarization, CIDEP (see Section 12.3.3) on F and G pairs of radicals formed under photolysis of a common termo- and photoinitiator 2,2 -azobis(2-methylpropionitrile) (AIBN) led to a tentative conclusion that initial spatial separation of 2-cyano-2-propyl radicals does not depend upon viscosity However, it is plausible that the diamagnetic dinitrogen molecule formed under photolysis of AIBN (and is invisible by ESR) separates further from a contact RP under photolysis in solvents of lower viscosity. The problem of initial spatial separation and mutual orientation ofradicals under photolysis still waits experimental elucidation. 

Transition metal-carbonyl-diimine complexes [Ru(E)(E ) (CO)2(a-diimine)] (E, E = halide, alkyl, benzyl, metal fragment a-diimine = 1, 4-diazabutadiene or 2,2 -bipyridine) are widely studied for their unconventional photochemical, photophysical, and electrochemical properties. These molecules have a great potential as luminophores, photosensitizers, and photoinitiators of radical reactions and represent a challenge to the understanding of excited-state dynamics. The near-UV/visible electronic spectroscopy of [Rn(X)(Me)(CO)2(/Pr-DAB)] (X = Cl or I iPr-DAB = A,A -di-isopropyl-l,4-diaza-l,3-butadiene) has been investigated throngh CASSCF/C ASPT2 and TD-DFT calculations on the model complexes [Ru(X)(Me)(CO)2(Me-DAB)] (X = Cl or I) (Table 2). 

Photoinitiated and optical electron-transfer processes and their relationship to corresponding ground-state thermal processes provide important new tests of theory, especially when comparisons are made for a given DBA system, of charge separation (CS) and charge recombination (CR), or of thermal and optical electron transfer (e.g., [27]). Photoinitiated processes have also been valuable in providing access to the dynamics of electron transfer in the activationless and inverted kinetic regimes (e.g., [43, 44]). 

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. 

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