Polarizabilities of the alkali anions: Li− to Fr−

Lupinetti, Concetta; Thakkar, Ajit J.

doi:10.1063/1.2393225

Cited by 9 publications

(3 citation statements)

References 60 publications

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“…From the comparison with the recommended or literature values, for group 2 atoms, the effects of the diffuse functions are much smaller than the error bar of the recommended values. For group 1 anions, our values for the augmented basis sets are much closer to the literature value than those for the nonaugmented sets. By adding only one well-optimized diffuse basis function in each angular orbital symmetry, the large variation between the v2z basis set and the v4z basis set is reduced from 40% to less than 1%.…”

Section: Applicationssupporting

confidence: 80%

Diffuse Basis Functions for Relativistic s and d Block Gaussian Basis Sets

Tecmer

Sunaga

2022

J. Chem. Theory Comput.

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Diffuse s, p, and d functions have been optimized for use with previously reported relativistic basis sets for the s and d blocks of the periodic table. The functions were optimized on the 4:1 weighted average of the s2 and p2 configurations of the anion, with the d shell in the d n+1 configuration for the d blocks. Exponents were extrapolated for groups 2 and 12, which have unstable or weakly bound anions. The diffuse basis sets have been tested by application to calculations of electron affinities of the group 11 elements (Cu, Ag, and Au), double electron affinities of the group 11 monocations, and potential energy curves of Mg2 and Ca2 van der Waals dimers, as well as some response properties of the group 1 anions (Rb–, Cs–, and Fr–), the group 2 elements (Sr, Ba, and Ra), and RbLi, CsLi, and FrLi molecules.

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Section: Applicationssupporting

confidence: 80%

Diffuse Basis Functions for Relativistic s and d Block Gaussian Basis Sets

Tecmer

Sunaga

2022

J. Chem. Theory Comput.

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“…There is the well-known break in monotonous changes in atomic properties of alkali metal atoms between Cs and Fr, usually attributed to relativistic effects [21]. The reported experimental value of the polarizability radius, r a (Fr) = 365 pm decreases relative to that of Cs (391 pm).…”

Section: Electronic Configurations Of Atomsmentioning

confidence: 91%

Atomic sizes from atomic interactions

Ganguly

2009

Journal of Molecular Structure

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“…͑14͒ with 253 CI-product basis states to calculate the polarizability of 2EM gas-phase sodide, we obtain a value of 1062a 0 3 , which is in excellent agreement with a previous CCSD͑T͒-level calculation that found ␣ = 1034Ϯ 10a 0 3 . 85 This means that sodide undergoes a dra-matic reduction in polarizability when interacting with the water solvent. This reduced polarizability in the liquid is particularly interesting given that the size of the anion in solution is roughly the same as in the gas phase: The calculated radii of gyration of Na − are 2.352Ϯ 0.004 and 2.299 Å in water ͑Table II͒ and in the gas phase, respectively.…”

Section: -11mentioning

confidence: 99%

The roles of electronic exchange and correlation in charge-transfer-to-solvent dynamics: Many-electron nonadiabatic mixed quantum/classical simulations of photoexcited sodium anions in the condensed phase

Glover

Larsen

Schwartz

2008

The Journal of Chemical Physics

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The charge-transfer-to-solvent (CTTS) reactions of solvated atomic anions serve as ideal models for studying the dynamics of electron transfer: The fact that atomic anions have no internal degrees of freedom provides one of the most direct routes to understanding how the motions of solvent molecules influence charge transfer, and the relative simplicity of atomic electronic structure allows for direct contact between theory and experiment. To date, molecular dynamics simulations of the CTTS process have relied on a single-electron description of the atomic anion-only the electron involved in the charge transfer has been treated quantum mechanically, and the electronic structure of the atomic solute has been treated via pseudopotentials. In this paper, we examine the severity of approximating the electronic structure of CTTS anions with a one-electron model and address the role of electronic exchange and correlation in both CTTS electronic structure and dynamics. To do this, we perform many-electron mixed quantum/classical molecular dynamics simulations of the ground- and excited-state properties of the aqueous sodium anion (sodide). We treat both of the sodide valence electrons quantum mechanically and solve the Schrodinger equation using configuration interaction with singles and doubles (CISD), which provides an exact solution for two electrons. We find that our multielectron simulations give excellent general agreement with experimental results on the CTTS spectroscopy and dynamics of sodide in related solvents. We also compare the results of our multielectron simulations to those from one-electron simulations on the same system [C. J. Smallwood et al., J. Chem. Phys. 119, 11263 (2003)] and find substantial differences in the equilibrium CTTS properties and the nonadiabatic relaxation dynamics of one- and two-electron aqueous sodide. For example, the one-electron model substantially underpredicts the size of sodide, which in turn results in a dramatically different solvation structure around the ion. The one-electron model also misses the existence of an entire manifold of bound CTTS excited states and predicts an absorption spectrum that is blueshifted from that in the two-electron model by over 2 eV. Even the use of a quantum mechanics/molecular mechanics (QM/MM)-like approach, where we calculated the electronic structure with our CISD method using solvent configurations generated from the one-electron simulations, still produced an absorption spectrum that was shifted approximately 1 eV to the blue. In addition, we find that the two-electron model sodide anion is very polarizable: The instantaneous dipole induced by local fluctuating electric fields in the solvent reaches values over 14 D. This large polarizability is driven by an unusual solvation motif in which the solvent pushes the valence electron density far enough to expose the sodium cation core, a situation that cannot be captured by one-electron models that employ a neutral atomic core. Following excitation to one of the bound CTTS excited states,...

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Polarizabilities of the alkali anions: Li− to Fr−

Cited by 9 publications

References 60 publications

Diffuse Basis Functions for Relativistic s and d Block Gaussian Basis Sets

Diffuse Basis Functions for Relativistic s and d Block Gaussian Basis Sets

Atomic sizes from atomic interactions

The roles of electronic exchange and correlation in charge-transfer-to-solvent dynamics: Many-electron nonadiabatic mixed quantum/classical simulations of photoexcited sodium anions in the condensed phase

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