An accurate model potential for alkali neon systems

Zanuttini, D.; Jacquet, E.; Giglio, E.; Douady, J.; Gervais, B.

doi:doi:10.1063/1.3269801

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Accurate dipole polarizabilities for water clusters n = 2–12 at the coupled-cluster level of theory and benchmarking of various density functionals

The static dipole polarizabilities of water clusters (2 ≤ N ≤ 12) are determined at the coupled-cluster level of theory (CCSD). For the dipole polarizability of the water monomer it was determined that the role of the basis set is more important than that of electron correlation and that the basis set augmentation converges with two sets of diffuse functions. The CCSD results are used to benchmark a variety of density functionals while the performance of several families of basis sets (Dunning,...

Introducing sampling entropy in repository based adaptive umbrella sampling

Determining free energy surfaces along chosen reaction coordinates is a common and important task in simulating complex systems. Due to the complexity of energy landscapes and the existence of high barriers, one widely pursued objective to develop efficient simulation methods is to achieve uniform sampling among thermodynamic states of interest. In this work, we have demonstrated sampling entropy (SE) as an excellent indicator for uniform sampling as well as for the convergence of free energy s...

We present a detailed investigation of the ground and lowest excited states of M-Ne dimers, for M = Li, Na, and K. We show that the potential energy curves of these Van der Waals dimers can be obtained accurately by considering the alkali neon systems as one-electron systems. Following previous authors, the model describes the evolution of the alkali valence electron in the combined potentials of the alkali and neon cores by means of core polarization pseudopotentials. The key parameter for an accurate model is the M⁺-Ne potential energy curve, which was obtained by means of ab initio CCSD(T) calculation using a large basis set. For each MNe dimer, a systematic comparison with ab initio computation of the potential energy curve for the X, A, and B states shows the remarkable accuracy of the model. The vibrational analysis and the comparison with existing experimental data strengthens this conclusion and allows for a precise assignment of the vibrational levels.

Article Outline

INTRODUCTION
MODEL POTENTIAL
AB INITIO CALCULATIONS
1. Theoretical methods
2. M⁺Ne potential energy
RESULTS
1. LiNe
2. NaNe
3. KNe
CONCLUSION

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KEYWORDS and PACS

Keywords

ab initio calculations, coupled cluster calculations, excited states, ground states, lithium compounds, potassium compounds, potential energy surfaces, quasimolecules, sodium compounds, vibrational states

PACS

31.50.Df

Potential energy surfaces for excited electronic states
31.15.A-

Ab initio calculations
33.20.Tp

Vibrational analysis
33.15.Mt

Rotation, vibration, and vibration-rotation constants
31.15.bw

Coupled-cluster theory

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http://dx.doi.org/10.1063/1.3269801

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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