Electron induced chemistry of metal-containing precursor molecules is central in focused electron beam induced deposition (FEBID). While some elementary processes leading to precursor decomposition were quantitatively characterized, data for neutral dissociation is missing. We provide this data for the model precursor Pt(PF3)4 by using the available cross sections for electronic excitation and ...

All-electron CCSD(T), QCISD(T) and MP4(SDQ) calculations including relativistic effects via the use of the IORAmm Hamiltonian have been performed for PdCO. The optimized molecular geometry is in nice agreement with the recently obtained experimental data. The Pd–CO bond dissociation energy is estimated to be 38.8 kcal/mol. The vibrational spectrum of PdCO is calculated and a reassessment of the...

With the high accuracy afforded by the sextuple correlation consistent basis set of Dunning, we have calculated energy levels, dissociation energies, equilibrium distances, and other spectroscopic constants for eleven valence and four Rydberg states of the CH radical. Comparisons with experimental and previous theoretical results are made for each state that has been treated. An understanding o...

The state-selective photodissociation of methylnitrite CH30NO(So,v) + hv -+ CH30+ NO(t,r,v) is reviewed and the dynamics of the bond-breaking process is analysed in connection with an ab initio S1-potential energy surface of the parent molecule. Experimental and theoretical results reveal an interesting picture of the dissociation path of a polyatomic molecule which decays by vibrational predis...

We examine the interaction between NO and the Rh(110) surface using ab initio DFT–LDA pseudo-potential plane-wave total energy calculations. Four different adsorption sites for perpendicular NO are considered. The short-bridge site with linear NO is found to be the optimal adsorption configuration. It is also possible for NO to bond parallel to the surface, and this may be the precursor to NO d...

Photodissociation of the ozone molecule at 193.4 nm (6.41 eV) and 157.6 nm (7.87 eV) is studied by fast-beam translational spectroscopy. Coincident detection of the dissociation products allows direct observation of the 3-fragment channel and determination of its kinematic parameters. The results indicate that at each wavelength, 3-fragment dissociation proceeds through synchronous concerted bo...

Hydrogen atom transfer is one important reaction in biological system, industry, and atmosphere. The preluded by hydrogen bond dissociation. To gain a comprehensive understanding on the reaction, it necessary to investigate how current computational methods model As starting point, we utilized density functional theory-based calculations identify effect of dispersion long-range corrections O—H ...

The O–H bond breaking in H2O molecules on metal surfaces covered with pre-adsorbed oxygen atoms is an important topic in heterogeneous catalysis. The adsorption configurations of H2O and relevant dissociation species on clean and O-pre-adsorbed Fe(100) surfaces were investigated by density functional theory (DFT). The preferential sites for H2O, HO, O, and H were investigated on both surfaces. ...

Cyanine borate (R(Ph)3B-; R alkyl) salts dissolved in non-polar solvents exist predominantly as ion pairs. Irradiation of the ion pair with visible light absorbed by the cyanine leads to formation of a locally excited singlet state of the dye. The singlet excited cyanine in the ion pair is capable of oxidizing the borate anion to the boranyl radical (R(Ph)3B.) The rate constant for this electro...

We derive an exact representation of the exchange-correlation energy within density functional theory (DFT) which spawns a class of approximations leading to correct long-range asymptotic behavior. Using a simple approximation, we develop an electronic structure theory that combines a new local correlation energy (based on Monte Carlo calculations applied to the homogeneous electron gas) and a ...