Classical trajectory calculations have been carried out to simulate the unimolecular decomposition of formaldehyde in the ground electronic state (Se). Global potential-energy surfaces were constructed using the empirical valence-bond (EVB) approach. Two sets of ab initio input were used to characterize two different EVB potential-energy surfaces, and trajectory calculations using one of these ...

Using van der Waals-corrected density functional theory and a local chemical bond analysis, we study and explain trends in the binding between CO2 and open-metal coordination sites within a series of two metal-organic frameworks (MOFs), BTT, and MOF-74 for Ca, Mg, and nine divalent transition-metal cations. We find that Ti and V result in the largest CO2 binding energies and show that for these...

Multistate empirical valence bond (EVB) models provide an accurate description of the energetics of proton transfer and solvation in complex molecular systems and can be efficiently used in molecular dynamics computer simulations. Within such models, the location of the moving protonic charge can be specified by the so-called center of charge, defined as a weighted average over the diabatic sta...

Predissociation dynamics of methylamines (CH(3)NH(2) and CH(3)ND(2)) on the first electronically excited states are studied using the slow-electron velocity imaging method to unravel the multi-dimensional nature of the N-H(D) chemical bond dissociation reaction which occurs via tunnelling. The nearly free internal rotation around the C-N bond axis is found to be strongly coupled to the reaction...

Molecules containing divalent sulfur can participate in significant noncovalent interactions. Computing accurate noncovalent interaction energies using ab initio quantum chemical methods requires a proper description of electron correlation effects. Coupled-cluster theory with single and double substitutions and perturbative triple substitutions, CCSD(T), using extrapolation to the complete bas...

An accurate system-bath model to investigate the quantum dynamics of hydrogen atoms chemisorbed on graphene is presented. The system comprises a hydrogen atom and the carbon atom from graphene that forms the covalent bond, and it is described by a previously developed 4D potential energy surface based on density functional theory ab initio data. The bath describes the rest of the carbon lattice...