The dissociative adsorption of N2 on W(110) is studied using classical dynamics on a six-dimensional potential energy surface obtained from density functional theory calculations. Two distinct channels are identified in the dissociation process: a direct one and an indirect one. It is shown that the direct channel is inhibited for low energy molecules (Ei < 400 meV) and low incidence angles. Th...

Calculations are discussed which characterize all the vibrational bound states of the H3 and D2H C molecular ions using a realistic ab initio potential energy surface. Graphical analysis and calculation of rotational constants show that both ions support a series of atom–diatom-like long-range states: asymptotic vibrational states. The role of these states in the H3 system and other molecules i...

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In the static field limit, the vibrational hyperpolarizability consists of two contributions due to: ~1! the shift in the equilibrium geometry ~known as nuclear relaxation!, and ~2! the change in the shape of the potential energy surface ~known as curvature!. Simple finite field methods have previously been developed for evaluating these static field contributions and also for determining the e...

Reaction paths and classical and quantum trajectories are studied within a generalized HamiltonJacobi framework, which allows to put on equal footing topology and dynamics in chemical reactivity problems. In doing so, we show how high-dimensional problems could be dealt with by means of Carathéodory plots or how trajectory-based quantum-classical analyses reveal unexpected discrepancies. As a w...

Ab inido molecular orbital ealenlations with large, polarizetion basis sets and incorporating valence electron correlation have been employed to examine the [GHzO]+' potential energy snrface. Four [WzO1+' isomers have been identified as potentially stable, observable ions. T h e are the experimentdly well-known ketene radical cation, [CH4=0 ]+ ' (a), and tbe presently unlmown ethynol radical ca...

Methods: Following upon the work presented in Ref. [1], quadrupole-constrained Hartree-Fock calculations are used to create a potential energy surface. An isomeric state and a state beyond the second barrier peak are excited by means of instantaneous as well as temporally extended gauge boosts with quadrupole shapes. The subsequent deexcitation is studied in a time-dependent Hartree-Fock simula...

A theory of the competition between fusion and quasi-fission in a heavy fusing system is proposed, which is based on a master equation and the two-center shell model. Fusion and quasi-fission arise from a diffusion process in an ensemble of nuclear shapes evolving towards the thermal equilibrium. The master equation describes the diffusion of the nuclear shapes due to quantum and thermal fluctu...

Potential energy surfaces of N,N-hydrogen migration of pyrazole and 5-methyl pyrazole for the ground and triplet states were calculated by the ab initio molecular orbital methods. All potential energy surfaces for the N.N-hydrogen shift have high energy barriers. The occurrence of the structural change indispensable to the switching function is doubtful for pyrazole and 5-methyl pyrazole. The s...

Jeffrey T. Scruggs Lamine Mili The Bradley Department of Electrical and Computer Engineering Virginia Polytechnic Institute and State University Blacksburg, VA 24061-0111 Abstract – In methods for assessing the critical clearing time based on the transient energy function, the dominant procedures in use for detecting the exit point across the Potential Energy Boundary Surface (PEBS) are the ray...