The three-body dissociation of I 2 (CO2) following excitation of the I 2 chromophore to the repulsive A Pg,1/2 and BRg;1=2 electronic states at 1.72 and 3.21 eV has been investigated using fast beam photofragment translational spectroscopy. The translational energy distributions for three-body dissociation provide a direct measurement of the CO2 binding energy, yielding a value of 218 ± 10 meV....

The dissociation of the hydroxymethyl radical, CH(2)OH, and its isotopolog, CD(2)OH, following the excitation of high OH stretch overtones is studied by quasi-classical molecular dynamics calculations using a global potential energy surface (PES) fitted to ab initio calculations. The PES includes CH(2)OH and CH(3)O minima, dissociation products, and all relevant barriers. Its analysis shows tha...

A series of iso-structural complexes [(SIPr)AgX] (X = Cl, Br, I, OTf; SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolidene) were synthesised, including the first example of a N-heterocyclic carbene silver(I) complex containing an O-bound triflate. Bond Energy Dissociation and Natural Orbitals for Chemical Valence bond analyses (BEDA & ETS-NOCV) revealing a significant NHC → M σ-back-donation, whi...

The photodissociation dynamics of methylamines (CH(3)NH(2) and CD(3)ND(2)) on the first electronically excited state has been investigated using the velocity map ion imaging technique probing the H or D fragment. Two distinct velocity components are found in the H(D) translational energy distribution, implying the existence of two different reaction pathways for the bond dissociation. The high ...

We have analyzed structure, stability, and Ru-NO bonding of the trans-[RuCl(NO)(NH3)4]2+ complex by using relativistic density functional theory. First, we focus on the bond dissociation energies associated with the three canonical dissociation modes leading to [RuCl(NH3)4]++NO+, [RuCl(NH3)4]2++NO, and [RuCl(NH3)4]3++NO-. The main objective is to understand the Ru-NO+ bonding mechanism in the c...

We present the result of a fragment-based energy decomposition analysis on some molecule-surface interactions. The analysis allows us to quantify the Pauli repulsion, its relief, and the attractive orbital interaction energy. In a metal, the existence of incompletely occupied energy bands causes significant relief of the Pauli repulsion due to escape of antibonding electrons to unoccupied state...

Several cardiotonic steroids have been modified by reduction of the unsaturated lactone and their interactions with the sodium- and potassium-activated ATPase ((Na+ + K+)-ATPase) have been investigated. Reduction of the unsaturated lactone results in a decrease in binding affinity due primarily to an increase in the dissociation rate constant concomitant with a decrease in the activation free e...

The dissociation of water is a key elementary step in many processes. From density functional theory, we show on several transition metal surfaces (Ru, Co, Rh, Ir, Ni, Pd and Pt) that water prefers to chemisorb as a H-bonded dimer, one molecule being chemisorbed by the O atom, but the second one developing only a weak interaction with the surface. Counterintuitively, the molecule in the dimer t...

Molecular dissociation under incident light whose energy is lower than the bond dissociation energy has been achieved through multi step excitation using a coupled state of a photon, electron, and multimode-coherent phonon as known as the dressed photon phonon (DPP). Here, we have investigated the effects of the DPP on CO2, a very stable molecule with high absorption and dissociation energies, ...

The homolytic bond dissociation energies of ZnO and ZnO + have been determined by using guided ion-beam mass spectrometry to measure the kinetic-energy dependence of the endothermic reactions of Zn + with nitrogen dioxide. The data are interpreted to yield the bond energy for ZnO, D g = 1.61 t 0.04 eV, a value considerably lower than previous experimental values, but in much better agreement wi...