Minimum moment required to bind a charged particle to an extended dipole

Mittleman, Marvin H.; Myerscough, V P

doi:10.1016/0031-9163(66)90400-8

Cited by 96 publications

(25 citation statements)

References 3 publications

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“…30 Indeed, it has been shown that such a potential with a dipole moment greater than 1.625 D possesses an infinite number of bound anionic states within the Born-Oppenheimer ͑BO͒ approximation. [29][30][31][32][33] Jordan and Luken demonstrated that the loosely bound electron in a dipole-bound state occupies a diffuse orbital localized mainly on the positive side of the molecular dipole. 34 The role of non-BO coupling has been studied by Garrett, who concluded that such couplings are negligible for dipole-bound states with electron binding energies (E bind ) much larger than molecular rotational constants.…”

Section: B Dipole-bound Anionsmentioning

confidence: 99%

Theoretical study of the dipole-bound anion (HPPH3)−

Skurski¹,

Gutowski²,

Simons³

1999

The Journal of Chemical Physics

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A theoretical prediction on intermolecular monoelectron dihydrogen bond H e H in the cluster anion ( FH ) 2 {e}( HF ) 2The possibility of electron binding to the HPPH 3 and H 2 PPH 2 tautomers of diphosphine was studied at the coupled cluster level of theory with single, double, and noniterative triple excitations. The HPPH 3 tautomer, with a dipole moment of 3.7 D, binds an electron by 333 cm Ϫ1 , whereas the H 2 PPH 2 tautomer forms neither a dipole-nor valence-bound anionic state. It is suggested that the HPPH 3 tautomer, which is kinetically stable but thermodynamically unstable relative to H 2 PPH 2 , may be formed by photodetachment from the P 2 H 4 Ϫ species examined in this work. An unusual aspect of the (HPPH 3 ) Ϫ anion is that electron correlation contributes 82% to the electronic stability and effects beyond the fourth order of the Mo "ller-Plesset perturbation theory contribute 55%.

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Section: B Dipole-bound Anionsmentioning

confidence: 99%

Theoretical study of the dipole-bound anion (HPPH3)−

Skurski¹,

Gutowski²,

Simons³

1999

The Journal of Chemical Physics

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“…Long-range dipolar binding plays an important role. Theoretically, a point dipole will bind an electron (and hence, alternatively, a positron) if its dipole moment is larger than a certain critical value, namely 1.625 D (39,40,41,42,43). The same is true of an extended structureless dipole (44), and of a point dipole surrounded by any charge distribution which is spherically symmetrical and overall neutral (42).…”

Section: Aamentioning

confidence: 90%

Theory of the Structures of Intermediates in Positronium Chemistry

Schrader

1979

Advances in Chemistry

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Different mechanisms for positron annihilation in a chemical medium are distinguished by different intermediates. All meas ured annihilation properties (lifetime, angular correlation, etc.) are in fact properties of that intermediate which exists just prior to annihilation. The structures of these inter mediates have been studied quantum mechanically as an adjunct to laboratory measurement of annihilation proper ties. The quantum mechanical studies involve calculating approximate wave functions for one-positron, many-electron systems. Some scattering states have been studied in this way for atoms, but all molecular studies so far focus on bound positrons or positronium atoms The questions of whether such bound states exist for particular molecules, and of the properties of those bound states which do exist, have been addressed in several studies. The most successful of these (1) permits one to examine positron/positronium -molecule interactions at a more fundamental level than was hitherto possible. P ositron/positronium (Ps) chemistry takes place somewhere between the beginning of the initial positron/Ps-reactant molecule encounter and annihilation. What happens in the intermediate region of the reaction coordinate is of great interest to the chemist. If we can understand this region at the level of positron/Ps interactions with individual molecules, we can map out the whole of positron/Ps chemistry. Our knowledge of this intermediate region is presently very hazy. The experimental literature contains many speculations about structures of intermediates. Frequently these speculations are quite sensible and are widely and uncritically accepted by the community, but are incorrect. A

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“…and 0 ϭ1.5 a.u. and the energetic splitting: energy in BOA E BO , second-order diagonal correction E (2)DK , second-order NA correction E (2)NA , total energy in second order E BO ϩE (2) , total energy in higher orders ͑only even orders are shown͒, and energy in the x-diabatic approximation, with the coupling between X and r treated exactly. We have seen that basis functions 5 and 6 hardly contribute to the exact wave function, while in BO approximation they should dominate in the tunneling region.…”

Section: ͑12͒mentioning

confidence: 99%

Double tunneling in dipole bound anions: A model study

Dufey

2004

The Journal of Chemical Physics

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Articles you may be interested inCombining ab initio quantum mechanics with a dipole-field model to describe acid dissociation reactions in water: First-principles free energy and entropy calculations J. Chem. Phys. 132, 074112 (2010); 10.1063/1.3317398Ab initio investigation of the electronic structure and bonding of BH, B H − , and HBBH moleculesThe applicability of the Born-Oppenheimer approximation for the description of the coupled nuclear and electronic tunneling dynamics in anionic dimers of hydrogen fluoride and water is studied. These complex molecules are modeled by a simpler system, with only one nuclear coordinate, which can be solved easily with arbitrary accuracy. Although the Born-Oppenheimer approximation is not applicable in a strict sense in the tunneling region where the electron becomes unbound, quite accurate values for the binding energy can be obtained when working with a discrete electronic basis. Employing a basis which is diabatic with respect to the angular coordinates, but adiabatic with respect to the radial coordinate, the convergence of a nonadiabatic perturbation expansion is also studied. Inclusion of the lowest-order nonadiabatic corrections reduces the error in the binding energy already by a factor of 10-20, while for the correct prediction of the tunneling splitting, it proves necessary to take into account higher-order corrections. With increasing number of diffuse functions included in the electronic basis, the nonadiabatic effects increase and the perturbation series converges more slowly.

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Minimum moment required to bind a charged particle to an extended dipole

Cited by 96 publications

References 3 publications

Theoretical study of the dipole-bound anion (HPPH3)−

Theoretical study of the dipole-bound anion (HPPH3)−

Theory of the Structures of Intermediates in Positronium Chemistry

Double tunneling in dipole bound anions: A model study

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