Correlation between hardness, polarizability, and size of atoms, molecules, and clusters

Ghanty, Tapan K.; Ghosh, Swapan K.

doi:10.1021/j100121a015

Cited by 251 publications

(155 citation statements)

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“…Since the geometries of clusters considered in this paper are, in general, not spherical in nature and thus such linear dependence of polarizabiliy with the volume of cluster is not very obvious. However, the studies on the relationship between the static polarizability and the volume of carbon and sodium clusters have already been reported in the literature [13,15,58] . Here we extend this study for potassium clusters and we go up to cluster containing 20 atoms.…”

Section: The Variation In the Different Ccsd(t) Results Is Attributedmentioning

confidence: 99%

Ab Initio Studies of Properties of Small Potassium Clusters

2008

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We have studied the structure and properties of potassium clusters containing even number of atoms ranging from 2 to 20 at the ab initio level. The geometry optimization calculations are performed using all-electron density functional theory with gradient corrected exchange-correlation functional. Using these optimized geometries we investigate the evolution of binding energy, ionization potential, and static polarizability with the increasing size of the clusters.

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Section: The Variation In the Different Ccsd(t) Results Is Attributedmentioning

confidence: 99%

Ab Initio Studies of Properties of Small Potassium Clusters

2008

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“…Global hardness describes the system's resistance on charge flow. It depends on its global charge, size and polarizability [51,52]. It is directly linked with the concept of chemical hardness and softness in HSAB principle [53][54][55].…”

Section: Theoretical Backgroundmentioning

confidence: 99%

Nucleophilic properties of purine bases: inherent reactivity versus reaction conditions

Stachowicz‐Kuśnierz

Korchowiec

2015

Struct Chem

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In the present study, nucleophilic properties of adenine and guanine are examined by means of density functional theory. H? is used as a model electrophile. Two modes of H ? attack on the bases are considered: on the neutral molecule and on the anion. Solvent effects are modeled by means of polarizable continuum model. Regioselectivity of attack is studied by analyzing two contributions. The first one is the energetic ordering of the tautomers. The second is the relative inherent reactivity of nucleophilic sites in the bases. Atomic softnesses calculated by means of charge sensitivity analysis are employed for this purpose. The most reactive sites in various tautomers are identified on the ground of Li-Evans model. For adenine, it is demonstrated that both in basic and in neutral pH N7 atom possesses the most nucleophilic character. In polar solvents, N7 substitution is also most favored energetically. In basic pH and nonpolar solvents as well as in the gas phase, N9 substitution is slightly more probable. For guanine, a mixture of N7-and N9-substituted products can be expected in basic pH. In neutral pH, inherent reactivity and energy trends are opposite to each other; therefore, the substitution does not occur. Experimentally observed products of reactions with various electrophiles and in various conditions confirm the results obtained in this study.

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“…The MPP was formulated on the basis of the MHP and an inverse relationship between hardness and polarizability. 14 This principle states that the natural direction of evolution of any system is towards a state of minimum polarizability. Both principles have been applied successfully to the study of molecular vibrations, 9,15-18 internal rotations, 6͑b͒,19 excited states, 20,21 aromaticity, 22 and different types of chemical reactions.…”

Section: Introductionmentioning

confidence: 99%

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

Torrent‐Sucarrat

Luis

Duran

et al. 2002

The Journal of Chemical Physics

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In a recent paper ͓J. Am. Chem. Soc. 123, 7951 ͑2001͔͒ we have shown for the first time the existence of molecules with nontotally symmetric vibrational modes that break the maximum hardness ͑MHP͒ and minimum polarizability ͑MPP͒ principles. We present here an extension of this previous work by devising a mathematical procedure that helps to determine the nontotally symmetric molecular distortions of a given molecule that do not follow the MPP or the MHP. This methodology is based on the diagonalization of the Hessian matrix of the polarizability or the hardness with respect to the vibrational normal coordinates. For a relatively large series of molecules, we have carried out diagonalizations of the Hessian matrix of the polarizability to determine the molecular distortions with a more marked MPP or anti-MPP character. From the results obtained, we have derived a set of simple rules that allow to predict a priori without calculations the existence of vibrational modes that break the MPP. With respect to the MHP, the results strongly depend on the method of calculation, but the same rules are useful to predict the existence of vibrational modes that disobey the MHP when the Koopmans' approximation is used to calculate the hardness.

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Correlation between hardness, polarizability, and size of atoms, molecules, and clusters

Cited by 251 publications

References 1 publication

Ab Initio Studies of Properties of Small Potassium Clusters

Ab Initio Studies of Properties of Small Potassium Clusters

Nucleophilic properties of purine bases: inherent reactivity versus reaction conditions

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

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