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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: In this article, the authors performed first-principles total energy calculations of low-dimensional sections of the electronically adiabatic potential energy surface (PES) that are relevant for the Eley-Rideal (ER) reaction of H atoms on a rigid Cu(111) surface.
Abstract: We have performed first-principles total-energy calculations of low-dimensional sections of the electronically adiabatic potential energy surface (PES) that are relevant for the Eley–Rideal (ER) reaction of H atoms on a rigid Cu(111) surface. These calculations were performed within density-functional theory using a plane-wave and pseudopotential method and the generalized gradient approximation for the exchange-correlation energy. The calculated energy points for various configurations of one and two atoms on the Cu(111) surface were used to construct a model PES that can be used in ER reaction dynamics calculations.
76 citations
TL;DR: Aguado et al. as discussed by the authors presented a new global fit for the potential energy surface of the LiFH system using time dependent treatment in reactant Jacobi coordinates in a body-fixed frame in which the internal coordinates are represented on a grid while Eulerian angles are described in a basis set.
Abstract: In this work we present a new global fit for the potential energy surface of the LiFH system This fit is an improvement of a recently published one [Aguado et al, J Chem Phys 106, 1013 (1997)] for which more ab initio points have been calculated (from 644 to 2323) The reaction dynamics is studied using a time dependent treatment in reactant Jacobi coordinates in a body-fixed frame in which the internal coordinates are represented on a grid while Eulerian angles are described in a basis set The centrifugal sudden approach is tested for total angular momentum J=5 and used to calculate the reaction cross section The reaction cross section shows oscillations as a function of kinetic energy This is a consequence of strong interference effects between reactant and product channels and is in agreement with the recent experimental data
76 citations
TL;DR: Electron density distribution computed using the MP2(FC), B3LYP, and Hartree-Fock methods with the same basis set is studied and it is found that ED topology does not depend on the method of calculation.
Abstract: The potential energy surface for the benzene dimer in stacked conformations (84 points calculated) was computed at the MP2(FC)∕6-31+G(2d,2p) level of theory. Electron density (ED) distribution computed using the MP2(FC), B3LYP, and Hartree–Fock methods with the same basis set is studied in the frame of topological analysis. It is found that ED topology does not depend on the method of calculation. The values of the ED and its Laplacian in the cage critical point calculated using different methods are determined to be linearly dependent with the slope depending on basis set. Correlation equations based on these properties allow the interaction energy between benzene rings to be predicted with 8% mean relative error in the energy for the given region of the potential energy surface. This provides a new method for the estimation of stacking interaction energy using ED properties calculated with low level quantum-chemical methods.
76 citations
TL;DR: An accurate theoretical prediction of the vibrational spectra for a pure nitrogen ring (cyclic-N(3)) molecule is obtained up to the energy of the (2)A(2)/(2)B(1) conical intersection and an unusually large magnitude of the geometric phase effects is found.
Abstract: An accurate theoretical prediction of the vibrational spectra for a pure nitrogen ring (cyclic-N3) molecule is obtained up to the energy of the 2A2/2B1 conical intersection. A coupled-channel approach using the hyperspherical coordinates and the recently published ab initio potential energy surface [D. Babikov, P. Zhang, and K. Morokuma, J. Chem. Phys. 121, 6743 (2004)] is employed. Two independent sets of calculations are reported: In the first set, the standard Born–Oppenheimer approximation is used and the geometric phase effects are totally neglected. In the second set, the generalized Born–Oppenhimer approximation is used and the geometric phase effects due to the D3h conical intersection are accurately treated. All vibrational states are analyzed and assigned in terms of the normal vibration mode quantum numbers. The magnitude of the geometric phase effect is determined for each state. One important finding is an unusually large magnitude of the geometric phase effects in the cyclic-N3: it is ∼100 c...
76 citations
TL;DR: The XMCQDPT2 results confirm the qualitative adequacy of the TDDFT (especially SF-TDDFT) picture of the excited stilbene but also reveal quantitative discrepancies that deserve further exploration.
Abstract: We report the detailed XMCQDPT2/cc-pVTZ study of trans–cis photoisomerization in one of the core systems of both experimental and computational photochemistry—the stilbene molecule. For the first time, the potential energy surface (PES) of the S1 state has been directly optimized and scanned using a multistate multiconfiguration second-order perturbation theory. We characterize the trans-stilbene, pyramidalized (phantom), and DHP-cis-stilbene geometric domains of the S1 state and describe their stationary points including the transition states between them, as well as S1/S0 intersections. Also reported are the minima and the activation barriers in the ground state. Our calculations correctly predict the kinetic isotope effect due to H/D exchange at ethylenic hydrogens, the dynamic behavior of excited cis-stilbene, and trans-cis branching ratio after relaxation to S0 through a rather unsymmetric conical intersection. In general, the XMCQDPT2 results confirm the qualitative adequacy of the TDDFT (especially...
76 citations