A comparison of Car—Parrinello and Born—Oppenheimer generalized valence bond molecular dynamics

Gibson, Douglas A; Ionova, Irina V.; Carter, Emily A.

doi:10.1016/0009-2614(95)00537-e

Cited by 65 publications

(43 citation statements)

References 21 publications

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“…Extending adiabatic ab initio molecular dynamics to the propagation of classical nuclei in a single non-interacting excited state is straightforward in the framework of wavefunction-based methods such as Hartree-Fock, 78-88 generalized valence bond (GVB), [89][90][91][92][93] multi-configuration self-consistent field (MCSCF), 79 complete active space SCF (CASSCF), 82,94,95 or full configuration interaction (FCI) 96 approaches. However, these methods are computationally rather demanding -even given present-day methods, algorithms, and hardware.…”

Section: Wavefunction-based Methodsmentioning

confidence: 99%

First Principles Molecular Dynamics Involving Excited States and Nonadiabatic Transitions

Doltsinis

Marx

2002

J. Theor. Comput. Chem.

147

169

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Extensions of traditional molecular dynamics to excited electronic states and non-Born-Oppenheimer dynamics are reviewed focusing on applicability to chemical reactions of large molecules, possibly in condensed phases. The latter imposes restrictions on both the level of accuracy of the underlying electronic structure theory and the treatment of nonadiabaticity. This review, therefore, exclusively deals with ab initio "on the fly" molecular dynamics methods. For the same reason, mainly mixed quantum-classical approaches to nonadiabatic dynamics are considered.

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Section: Wavefunction-based Methodsmentioning

confidence: 99%

First Principles Molecular Dynamics Involving Excited States and Nonadiabatic Transitions

Doltsinis

Marx

2002

J. Theor. Comput. Chem.

147

169

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“…This approach is often referred to as Born-Oppenheimer MD͑BOMD͒. It has been found recently 15 that trajectories obtained utilizing the BornOppenheimer approach can be both more accurate and less costly than their Car-Parrinello counterparts.…”

Section: Introductionmentioning

confidence: 98%

Hydrated proton clusters: Ab initio molecular dynamics simulation and simulated annealing

Wei

Salahub

1997

The Journal of Chemical Physics

129

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An ab initio molecular dynamics simulation technique is developed employing the Born–Oppenheimer (BO) approach in the framework of a Gaussian implementation of Kohn–Sham density functional theory (DFT). Simulation results for H5O2+ at 200 K are reported. The density profiles, autocorrelation functions and power spectra are presented. The anharmonic frequencies at 200 K are found to be close to the harmonic frequencies calculated directly from quantum methods at 0 K. Structures of large hydrated proton clusters are optimized. Simulated annealing techniques were employed to search for low energy structures and found to be very useful for clusters with 7–8 water molecules. A few very different structures with ground state energy 1–2 kcal/mol apart are shown. H3O+ is found to be the central unit of a few structures optimized. The ionic hydrogen bond was responsible for the stability of the H9O4+ unit in the large hydrated proton clusters. We also find structures with nascent H5O2+ units at the center whose energy is close to, sometimes even lower than that of the H3O+ centered structures. This can be used to explain the solvation facilitated proton transfer in clusters and in solution. The vibrational frequencies of the structures we optimized are tabulated and compared with the experimental results of Price et al. Questions are raised regarding their prediction of a new feature due to water molecules in the third solvation shell. Some new features have been observed for large clusters with heretofore unpredicted structures.

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“…Despite important progress in the numerical description of quantum dynamical processes in the condensed phase, [66][67][68][69][70][71][72][73][74] it is not yet possible to compute exactly the quantum mechanical ET rate in realistic simulations, and the incorporation of classical molecular dynamics is still necessary. There is, though, a well known drawback to any purely classical or mixed quantum/classical description of the process, which is known as the feedback problem.…”

Section: Discussionmentioning

confidence: 99%

Variational transition state theory for electron transfer reactions in solution

Benjamin

Pollak

1996

The Journal of Chemical Physics

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A comparison of Car—Parrinello and Born—Oppenheimer generalized valence bond molecular dynamics

Cited by 65 publications

References 21 publications

First Principles Molecular Dynamics Involving Excited States and Nonadiabatic Transitions

First Principles Molecular Dynamics Involving Excited States and Nonadiabatic Transitions

Hydrated proton clusters: Ab initio molecular dynamics simulation and simulated annealing

Variational transition state theory for electron transfer reactions in solution

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