We study the dissociative dynamics of O2 on Ag(110) by performing classical and quasiclassical trajectory calculations on an adiabatic six-dimensional potential energy surface (PES). The PES is constructed from the interpolation of a large set of energies that are calculated using spin-polarized density functional theory. The minimum energy barrier to dissociation amounts to 0.36 eV. This value...

Benchmark first principles calculations of the pure rotational and ro.vibrational transition frequencies and line strengths are presented, using two independent program suites. Both sets of calculations were performed using the same potential energy and dipole surfaces. Our example calculations use recently calculated surfaces for H 2S which have been shown to give good agreement with experimen...

An intermolecular potential energy surface for He(2)Br(2) complex in the ground state is calculated at the levels of fourth-order (MP4) Moller-Plesset and coupled-cluster [CCSD(T)] approximations, using large-core pseudopotential for Br atoms and the aug-cc-pV5Z basis set for He. The surface is characterized by three minima and the minimum energy pathways through them. The global minimum corres...

We study the dissociative adsorption of N(2) on W(100) and W(110) by means of density functional theory and classical dynamics. Working with a full six-dimensional adiabatic potential energy surface (PES), we find that the theoretical results of the dynamical problem strongly depend on the choice of approximate exchange-correlation functional for the determination of the PES. We consider the Pe...

The potential energy surfaces of the ground and valence excited states of both 3H-diazirine and diazomethane have been studied computationally by mean of the CASSCF method in conjunction with the cc-pVTZ basis set. The energies of the critical points found on such surfaces have been recomputed at the CASPT2/cc-pVTZ level. Additionally, ab initio direct dynamic trajectory calculations have been ...

We present a six-dimensional potential energy surface for the (H(2))(2) dimer based on coupled-cluster electronic structure calculations employing large atom-centered Gaussian basis sets and a small set of midbond functions at the dimer's center of mass. The surface is intended to describe accurately the bound and quasibound states of the dimers (H(2))(2), (D(2))(2), and H(2)-D(2) that correlat...

This paper calculates the potential energy curves of the 14 Λ-S and 49 Ω states, which come from the first three dissociation channels of the SiN- anion. These calculations are conducted using the valence internally contracted multireference configuration interaction and the Davidson correction approach. Core-valence correlation and scalar relativistic corrections are taken into account. The po...

The recently introduced method of correlation energy extrapolation by intrinsic scaling (CEEIS) is used to calculate the nonrelativistic electron correlations in the valence shell of the F(2) molecule at 13 internuclear distances along the ground state potential energy curve from 1.14 A to 8 A, the equilibrium distance being 1.412 A. Using Dunning's correlation-consistent double-, triple-, and ...

Benchmark full configuration interaction and equation-of-motion coupled-cluster model with single and double substitutions for ionized systems (EOM-IP-CCSD) results are presented for prototypical charge transfer species. EOM-IP-CCSD describes these doublet systems based on the closed-shell reference and thus avoids the doublet instability problem. The studied quantities are associated with the ...

We present a general theory of atomistic dynamical response in surface probe microscopy when two solid surfaces move with respect to each other in close proximity, when atomic instabilities are likely to occur. These instabilities result in a bistable potential energy surface, leading to temperature dependent atomic scale topography and damping (dissipation) images. The theory is illustrated on...