Effect of solvent motions on the dynamics of the Diels-Alder reaction.

How solvent motions affect the dynamics of chemical reactions in which the solute undergoes a substantial shape change is a fundamental but elusive issue. This work utilizes reactive simulation and Grote-Hynes theory to explore the effect of solvent motions on the dynamics of the Diels-Alder reaction (in the reverse direction, this reaction involves very substantial solute expansion) in aprotic solvents. The results reveal that the solvent environment is not sufficiently constraining to influence transition state passage dynamics, with the calculated transmission coefficients being close to unity. Even when solvent motions are suppressed or artificially slowed down, the solvent only affects the reaction dynamics in the transition state region to a very small extent. The only notable effect of solvent occurs far from the transition state region and corresponds to caging of the reactants within the reactant well.

Electron-Withdrawing Effects in the Photodissociation of CH2ICl To Form CH2Cl Radical, Simultaneously Viewed Through the Carbon K and Chlorine L2,3 X-ray Edges.

A fundamental chlorine-containing radical, CH2Cl, is generated by the ultrafast photodissociation of CH2ICl at 266 nm and studied at both the carbon K edge (∼284 eV) and chlorine L2,3 edge (∼200 eV) by femtosecond X-ray transient absorption spectroscopy. The electronic structure of CH2Cl radical is characterized by a prominent new carbon 1s X-ray absorption feature at lower energy, resulting from a transition to the half-filled frontier carbon 2p orbital (singly occupied molecular orbital of the radical; SOMO). Shifts of other core-to-valence absorption features upon photodissociation of CH2ICl to yield ·CH2Cl indicate changes in the energies of core-level transitions of carbon and chlorine to the σ*(C-Cl) valence orbital. When the C-I bond breaks, loss of the electron-withdrawing iodine atom donates electron density back to carbon and shields the carbon 1s core level, resulting in a ∼0.8 eV red shift of the carbon 1s to σ*(C-Cl) transition. Meanwhile, the 2p inner shell of the chlorine atom in the radical is less impacted by the iodine atom removal, as demonstrated by the observation of a ∼0.6 eV blue shift of the transitions at the chlorine L2,3 edges, mainly due to the stronger C-Cl bond and the increased energy of the σ*(C-Cl) orbital. The results suggest that the shift in the carbon 1s orbital is greater than the shift in the σ*(C-Cl) orbital upon going from the closed-shell molecule to the radical. Ab initio calculations using the equation of motion coupled-cluster theory establish rigorous assignment and positions of the X-ray spectral features in the parent molecule and the location of the SOMO in the CH2Cl radical.