A new simple approach to the polarizability of atoms and ions using frontier orbitals from the Kohn-Sham density functional theory

Ghanty, Tapan K.; Ghosh, Swapan K.

doi:10.1016/0166-1280(96)04493-4

Cited by 11 publications

(7 citation statements)

References 37 publications

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“…9a shows the α r,Cs (0) values we inferred from lifetime measurements, van der Waals C 6 coefficients, and Porsev et al's calculated |D D1,Cs |. Our results are compared to ab initio calculations of α r,Cs (0) [47,48,64] as well as ab initio calculations of α core,Cs [77][78][79][80][81] to which we added α v + α cv . Also among the comparisons in Fig.…”

Section: Using Combinations Of α(0) and C 6 Measurements To Report α mentioning

confidence: 86%

“…(b): α r,Cs (0) values deduced by combining measured α Cs (0) [3] with either measured C 6,Cs [67], principal transition lifetime [57][58][59]63,76] and R Cs [52] measurements, or α p,Cs (0) inferred from calculated |D D1,Cs | [61] and measured R Cs [52]. These inferred values are compared to several theoretical calculations [47,48,64,[77][78][79][80][81] and Cs ion polarizability measurements [82][83][84][85]. The asterisk (*) indicates that the indicated references provided α core values which we converted to α r (0) values by adding α v + α cv = 1.81 − 0.72 = 1.09 (in atomic units).…”

Section: Using Combinations Of α(0) and C 6 Measurements To Report α mentioning

confidence: 99%

“…This includes α tail (0). Values in bold are used to produce the results presented in Table 2 [78] ( f ) (a) Calculated using f ik values from NIST [49] for n − n transitions with n = n + 1 to n + 5.…”

Section: Acknowledgementsmentioning

confidence: 99%

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Analysis of Polarizability Measurements Made with Atom Interferometry

Gregoire

Brooks

Trubko

et al. 2016

Atoms

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Abstract:We present revised measurements of the static electric dipole polarizabilities of K, Rb, and Cs based on atom interferometer experiments presented in [Phys. Rev. A 2015, 92, 052513] but now re-analyzed with new calibrations for the magnitude and geometry of the applied electric field gradient. The resulting polarizability values did not change, but the uncertainties were significantly reduced. Then, we interpret several measurements of alkali metal atomic polarizabilities in terms of atomic oscillator strengths f ik , Einstein coefficients A ik , state lifetimes τ k , transition dipole matrix elements D ik , line strengths S ik , and van der Waals C 6 coefficients. Finally, we combine atom interferometer measurements of polarizabilities with independent measurements of lifetimes and C 6 values in order to quantify the residual contribution to polarizability due to all atomic transitions other than the principal ns-np J transitions for alkali metal atoms.

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Section: Using Combinations Of α(0) and C 6 Measurements To Report α mentioning

confidence: 86%

Section: Using Combinations Of α(0) and C 6 Measurements To Report α mentioning

confidence: 99%

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Analysis of Polarizability Measurements Made with Atom Interferometry

Gregoire

Brooks

Trubko

et al. 2016

Atoms

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“…the polarizability (a.u.) of P (24.5), P 2+ (9.6), P 3+ (7.2), P 4+ (4.5) 123 ), and the inverse effect upon electron attachment, (@ 3 E/dv( À r)dv( À r 0 )@N) is a futher example of a chemically relevant third order derivative.…”

Section: Third Order Derivatives; More Relevant Than Expectedmentioning

confidence: 99%

Conceptual DFT: the chemical relevance of higher response functions

Geerlings

Proft

2008

Phys. Chem. Chem. Phys.

275

193

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In recent years conceptual density functional theory offered a perspective for the interpretation/prediction of experimental/theoretical reactivity data on the basis of a series of response functions to perturbations in the number of electrons and/or external potential. This approach has enabled the sharp definition and computation, from first principles, of a series of well-known but sometimes vaguely defined chemical concepts such as electronegativity and hardness. In this contribution, a short overview of the shortcomings of the simplest, first order response functions is illustrated leading to a description of chemical bonding in a covalent interaction in terms of interacting atoms or groups, governed by electrostatics with the tendency to polarize bonds on the basis of electronegativity differences. The second order approach, well known until now, introduces the hardness/softness and Fukui function concepts related to polarizability and frontier MO theory, respectively. The introduction of polarizability/softness is also considered in a historical perspective in which polarizability was, with some exceptions, mainly put forward in non covalent interactions. A particular series of response functions, arising when the changes in the external potential are solely provoked by changes in nuclear configurations (the "R-analogues") are also systematically considered. The main part of the contribution is devoted to third order response functions which, at first sight, may be expected not to yield chemically significant information, as turns out to be for the hyperhardness. A counterexample is the dual descriptor and its R analogue, the initial hardness response, which turns out to yield a firm basis to regain the Woodward-Hoffmann rules for pericyclic reactions based on a density-only basis, i.e. without involving the phase, sign, symmetry of the wavefunction. Even the second order nonlinear response functions are shown possibly to bear interesting information, e.g. on the local and global polarizability. Its derivatives may govern the influence of charge on the polarizability, the R-analogues being the nuclear Fukui function and the quadratic and cubic force constants. Although some of the higher order derivatives may be difficult to evaluate a comparison with the energy expansion used in spectroscopy in terms of nuclear displacements, nuclear magnetic moments, electric and magnetic fields leads to the conjecture that, certainly cross terms may contain new, intricate information for understanding chemical reactivity.

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“…is: exothermic (DH \ 0), exotropic (DS \ 0) and spontaneous (DG \ 0). And as suggested by Ghanty and Ghosh [121] for a reaction of the type: A ? B ?…”

Section: Vibrational (Rotational) Spectra and Thermochemistrymentioning

confidence: 93%

From Democritus to Schrödinger: a reflection on quantum molecular modeling

Vasilescu

Adrian-Scotto

2010

Struct Chem

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This review describes the saga of the atom and molecules, from the atomic concept as it was introduced 25 centuries ago by Leucippus and Democritus, to the modern Quantum Molecular Modeling. Quantum methods that have given rise to the contemporary Molecular Modeling are briefly presented. Chosen examples illustrate the performance and the predictions of Quantum Modeling in the following topics: conformational analysis, electrostatics, molecular spins and radicals, infrared and Raman spectra, thermochemistry, and electrophilicity properties derived from the molecular chemical potential.

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A new simple approach to the polarizability of atoms and ions using frontier orbitals from the Kohn-Sham density functional theory

Cited by 11 publications

References 37 publications

Analysis of Polarizability Measurements Made with Atom Interferometry

Analysis of Polarizability Measurements Made with Atom Interferometry

Conceptual DFT: the chemical relevance of higher response functions

From Democritus to Schrödinger: a reflection on quantum molecular modeling

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