Post-transition state dynamics

Rehbein, J., Carpenter, B. K. (2011). Do we fully understand what controls chemical selectivity Physical Chemistry Chemical Physics, 13(41), 20906-20922. Illustrative examples Thomas, J. B., Waas, J. R., Harmata, M., Singleton, D. A. (2008). Control Elements in Dynamically Determined Selectivity on a Bifurcating Surface. Journal of the American Chemical Society, 130(44), 14544—14555. Hong., Y. J., TantiUo, D. J. (2014) Biosynthetic consequences of multiple sequential post-transition-state bifurcations. iVafun Chemistry, 6, 104—111. 

During the past four decades the dynamics and mechanisms of electron-transfer processes have been studied via the application of transition-state theory to the kinetics for electrochemical processes. As a result, both the kinetics of the electron-transfer processes (from solid electrode to the solution species) as well as of pre- and post-electron-transfer homogeneous processes can be characterized quantitatively. 

Since inclusion of dynamic electron correlation increases the importance of the aromatic contribution (Tgro ) at the expense of the diradical contributions, a single-reference post-HF method might be satisfactory. CCD and QCISD find a transition state with Rjg = 1.87 A. Both methods predict an activation barrier that is about 7 kcal moC too high. ... 

Boulon G (1987) Spectroscopy of post transition metal ions. In Di Bartolo B (ed) Spectroscopy of solid-state laser-type materials. Plenum Press, New York, pp 223-266 Boulon G (1997) Broad band centers applied for laser materials example of tetrahedrally coordinated centers, hi Di Bartolo B (ed) Spectroscopy and dynamics of collective excitations in solids. Plenum Press, London, New York, pp 561-573 Boulon G (2000) Transition metal ion lasers - Cr " ". In Webb C, Jones J (eds) Handbook of laser technology and application. Volume II. Laser design and laser systems. CRC Press, London, pp 307-337... 

Chemical dynamics simulations of the gas phase 5 2 reactions of methyl halides have been carried out at many different levels of theory and compared with experimental measurements and predictions based on transition state theory and RRKM (Rice-Ramsperger-Kassel-Marcus) theory. Although many 5 2 reactions occur by the traditional pre-reaction complex, transition state, post-reaction complex mechanism, three additional non-statistical mechanisms were detected when the F -CH3-I reaction was analysed at an atomic level (i) a direct rebound mechanism where F attacks the backside of the carbon and CH3-F separates (bounces off) from the iodine ion, (ii) a direct stripping mechanism where F approaches CH3-I from the side and strips away the CH3 group, and (iii) an indirect reaction where the pre-reaction complex activates the C-I bond causing a CH3-I rotation and then the 5 2 reaction. The presence of these processes demonstrate that three non-statistical effects, (i) recrossing of the transition state is important, (ii) the transfer of the translational energy from the reactants into the rotational and vibrational modes of the substrate is inefficient, and (iii) there is... 

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