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Potential energy surface

About: Potential energy surface is a research topic. Over the lifetime, 11674 publications have been published within this topic receiving 307691 citations.


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TL;DR: It is shown that the reactivity depends on the site of impact in a complex fashion controlled by the topography of the potential energy surface rather than the barrier height alone, as predicted by the recently proposed sudden vector projection model.
Abstract: The dissociative chemisorption of water on rigid Ni(111) is investigated using a quasiclassical trajectory method on a nine-dimensional global potential energy surface based on a faithful permutation invariant fit of $\ensuremath{\sim}25\text{ }000$ density functional theory points. This full-dimensional model not only confirms the validity of our earlier reduced-dimensional model with 6 degrees of freedom, but also allows the examination of the influence of impact sites and incident angles. It is shown that the reactivity depends on the site of impact in a complex fashion controlled by the topography of the potential energy surface rather than the barrier height alone. In addition, the reaction is promoted by momenta both parallel and perpendicular to the surface, as predicted by the recently proposed sudden vector projection model.

91 citations

Journal ArticleDOI
TL;DR: In this article, the authors analyzed the linear H⊗(g⊕2h) Jahn-Teller problem with respect to the instability of icosahedral molecules in fivefold degenerate states.
Abstract: The linear H⊗(g⊕2h) Jahn–Teller problem, relevant to the instability of icosahedral molecules in fivefold degenerate states, is analyzed in detail for the first time. The method of the isostationary function is used to identify all the extrema of the corresponding potential energy surface. Depending on one single mode‐splitting parameter, two different coupling regimes are possible, favoring either pentagonal or trigonal minima. The saddle points on interconversion paths between equivalent minima are identified and the topology of the low‐energy regions of the surface is determined. The results are found to be in agreement with the epikernel principle. In addition the symmetry characteristics of the principal warping term under the SO(5) symmetry group of electronic space are assigned.

90 citations

Journal ArticleDOI
TL;DR: A full dimensional, ab initio based potential energy surface for CH(5) (+) and the dipole moment surfaces are fit using novel procedures that ensure the full permutational symmetry of the system.
Abstract: We report a full dimensional, ab initio based potential energy surface for CH5+. The ab initio electronic energies and gradients are obtained in direct-dynamics calculations using second-order Moller-Plesset perturbation theory with the correlation consistent polarized valence triple zeta basis. The potential energy and the dipole moment surfaces are fit using novel procedures that ensure the full permutational symmetry of the system. The fitted potential energy surface is tested by comparing it against additional electronic energy calculations and by comparing normal mode frequencies at the three lowest-lying stationary points obtained from the fit against ab initio ones. Well-converged diffusion Monte Carlo zero-point energies, rotational constants, and projections along the CH and HH bond lengths and the tunneling coordinates are presented and compared with the corresponding harmonic oscillator and standard classical molecular dynamics ones. The delocalization of the wave function is analyzed through c...

90 citations

Journal ArticleDOI
TL;DR: In this paper, a time-dependent quantum dynamics calculation is reported for the O( 1 D) + H 2 reaction in three dimensions, and the calculated cross sections are in generally good agreement with an earlier classical trajectory calculation of Schinke and Lester.

90 citations

Journal ArticleDOI
TL;DR: Structural, dynamical, and response properties of liquid water calculated by ab initio molecular dynamics using the embedded-fragment spin-component-scaled second-order many-body perturbation method with the aug-cc-pVDZ basis set are presented.
Abstract: A direct, simultaneous calculation of properties of a liquid using an ab initio electron-correlated theory has long been unthinkable. Here we present structural, dynamical, and response properties of liquid water calculated by ab initio molecular dynamics using the embedded-fragment spin-component-scaled second-order many-body perturbation method with the aug-cc-pVDZ basis set. This level of theory is chosen as it accurately and inexpensively reproduces the water dimer potential energy surface from the coupled-cluster singles, doubles, and noniterative triples with the aug-cc-pVQZ basis set, which is nearly exact. The calculated radial distribution function, self-diffusion coefficient, coordinate number, and dipole moment, as well as the infrared and Raman spectra are in excellent agreement with experimental results. The shapes and widths of the OH stretching bands in the infrared and Raman spectra and their isotropic-anisotropic Raman noncoincidence, which reflect the diverse local hydrogen-bond environment, are also reproduced computationally. The simulation also reveals intriguing dynamic features of the environment, which are difficult to probe experimentally, such as a surprisingly large fluctuation in the coordination number and the detailed mechanism by which the hydrogen donating water molecules move across the first and second shells, thereby causing this fluctuation.

90 citations


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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
2023128
2022206
2021288
2020322
2019295
2018310