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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 considered the case that the motion of the system is on a single potential energy surface and the case where this motion occurred on two surfaces was considered elsewhere.
Abstract: Intramolecular charge transfer are considered for the case that the motion of the system is on a single potential energy surface. The case where this motion occurred on two surfaces was considered elsewhere. The former is shown to be much preferable for studies of solvent dynamics. Several aspects of the relation between ‘‘constant charge’’ dielectric relaxation time of the polar solvent and the experimental decay time of emission from the polar excited state of the solute are discussed for hydrogen‐bonded systems.
183 citations
TL;DR: The results show very good agreement with density functional theory calculations, reproducing the individual CSOV energy contributions for a given interaction as well as the B3LYP total interaction energies with errors below kBT at room temperature.
Abstract: Total intermolecular interaction energies are determined with a first version of the Gaussian electrostatic model (GEM-0), a force field based on a density fitting approach using s-type Gaussian functions. The total interaction energy is computed in the spirit of the sum of interacting fragment ab initio (SIBFA) force field by separately evaluating each one of its components: electrostatic (Coulomb), exchange repulsion, polarization, and charge transfer intermolecular interaction energies, in order to reproduce reference constrained space orbital variation (CSOV) energy decomposition calculations at the B3LYP/aug-cc-pVTZ level. The use of an auxiliary basis set restricted to spherical Gaussian functions facilitates the rotation of the fitted densities of rigid fragments and enables a fast and accurate density fitting evaluation of Coulomb and exchange-repulsion energy, the latter using the overlap model introduced by Wheatley and Price [Mol. Phys. 69, 50718 (1990)]. The SIBFA energy scheme for polarization and charge transfer has been implemented using the electric fields and electrostatic potentials generated by the fitted densities. GEM-0 has been tested on ten stationary points of the water dimer potential energy surface and on three water clusters (n=16,20,64). The results show very good agreement with density functional theory calculations, reproducing the individual CSOV energy contributions for a given interaction as well as the B3LYP total interaction energies with errors below kBT at room temperature. Preliminary results for Coulomb and exchange-repulsion energies of metal cation complexes and coupled cluster singles doubles electron densities are discussed.
183 citations
TL;DR: In this article, a quantum mechanical method is described for calculating state-selected cross sections and rate constants for four-atom reactions of the general form AB+CD→ABC+D with nonlinear geometry.
Abstract: A quantum mechanical method is described for calculating state‐selected cross sections and rate constants for four‐atom reactions of the general form AB+CD→ABC+D with nonlinear geometry. The method involves using hyperspherical coordinates to describe the BC and CD bonds, accounting for both the rotation of the AB molecule and the bending mode of the ABC molecule with a spherical harmonic basis set, holding the AB spectator bond length fixed and applying a version of the bending‐corrected‐rotating line approximation to treat the rotation of the CD molecule. The method is applied to the OH(j)+H2(v)→H2O(n,m)+H reaction, and its reverse reaction, where v and j are vibrational and rotational quantum numbers, and n and m label bending and local OH‐stretching vibrational states of the H2O molecule. A modified potential energy surface based on a fit to ab initio data is used. Comparisons of the calculated cross sections are made with quasiclassical trajectory calculations. The effect of the bending and stretchin...
183 citations
TL;DR: A novel method, designated as the density functional theory/coupled-cluster with single and double and perturbative triple excitation [DFT/CCSD(T)] correction scheme, was developed for precise calculations of weakly interacting sp(2) hydrocarbon molecules and applied to the benzene dimer.
Abstract: A novel method, designated as the density functional theory/coupled-cluster with single and double and perturbative triple excitation [DFT/CCSD(T)] correction scheme, was developed for precise calculations of weakly interacting sp(2) hydrocarbon molecules and applied to the benzene dimer. The DFT/CCSD(T) interaction energies are in excellent agreement with the estimated CCSD(T)/complete basis set interaction energies. The tilted T-shaped structure having C(s) symmetry was determined to be a global minimum on the benzene-dimer potential energy surface (PES), approximately 0.1 kcal/mol more stable than the parallel-displaced structure. A fully optimized set of ten stationary points on the benzene-dimer PES is proposed for the evaluation of the reliability of methods for the description of weakly interacting systems.
181 citations
TL;DR: In this paper, full-dimensional quantum mechanical calculations for the CH4+H→CH3+H2 reaction employing the Jordan-Gilbert potential energy surface have been reported.
Abstract: Accurate full-dimensional quantum mechanical calculations are reported for the CH4+H→CH3+H2 reaction employing the Jordan–Gilbert potential energy surface. Benchmark results for the thermal rate constant and the cumulative reaction probability are presented and compared to classical transition state theory as well as reduced dimensionality quantum scattering calculations. The importance of quantum effects in this system is highlighted.
181 citations