An electron–water pseudopotential for condensed phase simulation

Schnitker, Jürgen; Rossky, Peter J.

doi:10.1063/1.452002

Cited by 198 publications

(167 citation statements)

References 44 publications

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“…In particular, we note the pioneering work of Landman and co-workers, 74 Rossky et al, 75 Staib and Borgis, 76 and Berne and co-workers. 77 The key features of the models introduced by these researchers, as well as of a more recent model of Mosyak et al, 81 are summarized in Table IV.…”

Section: Applications Of the Drude Model To Water Clustersmentioning

confidence: 99%

“…75 This is a consequence of the small overlap between the orbital occupied by the excess electron and the charge distribution of the neutral molecules. We also adopt this approximation in the present treatment of electron-HCN and electron-HNC interactions.…”

Section: B Drude Model For Electron-polar Molecule Interactionsmentioning

confidence: 99%

“…8,21,22,35,62,148 It was long believed that theoretical methods allowing for the electrostatic interactions, and perhaps also, polarization of the water molecules by the excess electron, were adequate for describing (H 2 O) n -species. 21,22,[74][75][76][77]105 Within an ab initio electronic structure framework, this would lead one to believe that the Hartree-Fock method provides a good zeroth-order description of the wavefunction of the anion and of the electron binding energies of these species. This expectation has also served as the basis of several one-electron model approaches that have been developed for describing an excess electron interacting with water.…”

Section: General Considerationsmentioning

confidence: 99%

“…63,[74][75][76][77][78][79][80][81] In general, these approaches employ a standard classical force field for describing the interactions between the neutral monomers and a model potential for describing the interaction of the excess electron with the monomers. The excess electron is treated quantum mechanically.…”

Section: General Considerationsmentioning

confidence: 99%

“…This expectation has also served as the basis of several one-electron model approaches that have been developed for describing an excess electron interacting with water. [74][75][76][77]81 These model potentials have been used in Monte-Carlo and molecular dynamics simulations (MD) of excess electrons interacting with bulk water, water films, and water clusters. [128][129][130][131][132][133] Over the past few years it has been realized that dispersion interactions between an excess electron and the polar molecules in a cluster play a major role in the electron binding.…”

Section: General Considerationsmentioning

confidence: 99%

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A Drude-model approach to dispersion interactions in dipole-bound anions

Wang¹,

Jordan²

2001

The Journal of Chemical Physics

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A one-electron model potential for calculating the binding energy of an excess electron interacting with polar molecules and their clusters is described. The unique feature of this potential is the treatment of polarization and dispersion effects by means of a Drude model. The approach is tested by calculating the energies for binding an excess electron to HCN, (HCN)2, HNC, and (HNC)2. The model potential results are found to be in good agreement with the predictions of high-level all-electron calculations.

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Section: Applications Of the Drude Model To Water Clustersmentioning

confidence: 99%

Section: B Drude Model For Electron-polar Molecule Interactionsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

See 3 more Smart Citations

A Drude-model approach to dispersion interactions in dipole-bound anions

Wang¹,

Jordan²

2001

The Journal of Chemical Physics

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Cavity Model Challenged: The Hydrated Electron is Localized in Regions of Enhanced Water Density

Ludwig

Paschek

2010

ChemPhysChem

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Although the existence of a solvated electron in alkali metal solutions of liquid ammonia had been proposed already in 1907, [1] it took more than fifty years until the hydrated electron in water and in aqueous solutions was discovered by Hart and Boag.[2] A hydrated electron is formed when an extra electron is added to a cluster of water molecules [(H 2 O) n À ] or to the condensed phase. This excess electron in aqueous solution is a product of water radiolysis or direct electron irradiation and is a key reactive intermediate in many biological and chemical reactions, despite its short lifetime. Although the free electron in aqueous solutions (e À aq ) has been studied now for half a century, the understanding of electron hydration at a molecular level has persisted as one of the outstanding problems in contemporary chemical physics. In particular, it is still unclear how exactly the water molecules are arranged in its vicinity. Now Larsen et al. challenge the consensus "cavity model" for the hydrated electron.[3] In their calculations Larsen et al. found that the free electron forms a region that is effectively attracting water molecules by forming a delocalized electron cloud instead of excluding water by the formation of a localized cavity.Since its discovery, the spectral properties of the hydrated electron has been almost exclusively explained on the basis of the cavity model. The model is based on two assumptions. Firstly, it is assumed that the free electron is excluded from regions where the water molecules have distinct electron density, resulting in solvent cavities. Secondly, such a nearly spherical void is stabilized by hydrogen bonding to six water molecules in the first solvation shell, leading to an average radius of gyration for the cavity of about 0.24 nm (Figure 1). In this quasi-octahedral arrangement called the Kevan structure, one hydrogen atom of each water molecule in the first hydration shell points directly towards the center of mass (COM) of the hydrated electron. [4] In this cavity the hydrated electron is believed to occupy an s-type electronic ground state. However, for the structure determination of the hydrated electron, only indirect experimental methods are available. The cavity model is based on a broad asymmetric absorption band with a peak at about 1.7 eV. [5][6][7] The broad features in the red part of the visible spectrum are related to the excited state of the hydrated electron and can be thought of as a transition from the s-state to an excited p-state. Previous molecular dynamics simulations supported this cavity model, [8][9][10] largely because the pseudopotential between the excess electron and the water molecules is strongly attractive due to the positive partial charge of the H atoms. However, problems remained, because the cavity model could not account for the fast electronic relaxation kinetics of the excited state of the excess electron as measured by Yokoyama et al. [11] This deficit is now overcome by the model presented by Larsen et al. who re-examined the el...

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