scholarly journals Electron-pair bonding in real space. Is the charge-shift family supported?

2019 ◽  
Vol 55 (35) ◽  
pp. 5071-5074 ◽  
Author(s):  
J. Luis Casals-Sainz ◽  
F. Jiménez-Grávalos ◽  
E. Francisco ◽  
A. Martín Pendás

Charge-shift bonding (CSB) has been introduced as a distinct third family of electron-pair links that adds to the covalent and ionic tradition.

2014 ◽  
Vol 10 (6) ◽  
pp. 2410-2418 ◽  
Author(s):  
Huaiyu Zhang ◽  
David Danovich ◽  
Wei Wu ◽  
Benoît Braïda ◽  
Philippe C. Hiberty ◽  
...  

Author(s):  
Sason Shaik ◽  
David Danovich ◽  
Benoit Braida ◽  
Wei Wu ◽  
Philippe C. Hiberty

1996 ◽  
Vol 74 (6) ◽  
pp. 1106-1115
Author(s):  
Akitomo Tachibana

By projecting the BCS ground state of superconducting electron condensate on the N-electron Hilbert space, a real-space equation-of-motion is obtained for the electron pair function [Formula: see text] at absolute zero temperature (T = 0):[Formula: see text]where ρN−2 denotes electron density of the (N – 2)-electron condensate given as[Formula: see text]Since the exchange-correlation potential is given as an explicit functional of electron density, this equation represents the fundamental working equation for the new density functional theory of superconductivity. The 2nd-order density matrix ΓN(1, 2|1′, 2′) projected on the N-electron Hilbert space satisfies[Formula: see text]so that asymptotically[Formula: see text]where [Formula: see text] denotes the center-of-mass coordinate of electrons e1and e2; this is considered the ODLRO (off-diagonal long-range order) at T = 0 projected on the N-electron Hilbert space. A new attractive potential analysis for the two-electron scattering problem (A. Tachibana, Bull. Chem. Soc. Jpn. 66, 3319 (1993); Int. J. Quantum Chem. 49, 625 (1994)) is straightforwardly applicable to the present equation-of-motion, and we can also plug in the vibronic interaction for the enhancement of the attractive force. Our approach is purely mathematical and basic, restricted merely at T = 0, but proves to serve as a real-space analysis of the pair function itself. Key words: equation-of-motion of electron pair, BCS theory, superconductivity, electron pair function, density functional theory.


Crystals ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 564
Author(s):  
Daniel Duvinage ◽  
Enno Lork ◽  
Simon Grabowsky ◽  
Stefan Mebs ◽  
Jens Beckmann

The reaction of (6-Ph2P-Ace-5-)2P(O)H with (tht)AuCl3 proceeds via elimination of tetrahydrothiophene (tht) and HCl, providing the zwitterionic PPP-pincer complex (6-Ph2P-Ace-5-)2P(O)AuCl2 (1) as yellow crystals. The molecular structure of 1 was established and studied by X-ray crystallography. The electronic structure was computationally analyzed using a comprehensive set of real-space bonding indicators derived from electron and electron-pair densities, providing insight into the relative contributions of covalent and non-covalent forces to the polar-covalent Au–Cl, Au–P, and P–O− bonds; the latter being one of the textbook cases for strongly polarized covalent interactions. Partial spatial complementarity between both bonding aspects is suggested by the electronic properties of the distinctively different Au–Cl bonds.


1992 ◽  
Vol 114 (20) ◽  
pp. 7861-7866 ◽  
Author(s):  
Sason Shaik ◽  
Philippe Maitre ◽  
Gjergji Sini ◽  
Philippe C. Hiberty

1974 ◽  
Vol 52 (8) ◽  
pp. 1310-1320 ◽  
Author(s):  
R. Daudel ◽  
R. F. W. Bader ◽  
M. E. Stephens ◽  
D. S. Borrett

The reality of the electron pair as a fundamental unit in the electronic structure of molecular systems is evidenced by calculations which show that the most probable partitioning of a system is the one which localizes pairs of electrons in well-defined spatial regions or loges. The loges in turn, correspond to those regions of space generally associated with core, bonded, and non-bonded electrons. In terms of information theory, they yield the maximum amount of information concerning the localizability of the electrons. The most probable three-loge partitioning of the six-electron BH(X1∑+) system, for example, is dominated by the event which places two electrons in each of three loges, the location and shape of the loges being such as to justify the labelling of the electron pairs they localize as core, bonded and nonbonded. Since the loges are defined in real space and are totally nonoverlapping, one may define the volume of space occupied by pairs of electrons. In BH, for example, the volume of space required to contain 95% of the nonbonded pair of electrons is over two times larger than that required to contain 95% of the bonded pair. It is possible to define core loges which exhibit pair occupation probabilities ranging in value from 95% in LiH+ to 85% in BH. Corresponding probabilities ranging in value from 75% to 90% are obtained for bonded and nonbonded loges. In the set of molecules studied here, the occurrence of events with such high probabilities is found only for loges which maximize the probability of a pair occupation.


Molecules ◽  
2021 ◽  
Vol 26 (2) ◽  
pp. 513
Author(s):  
Julen Munárriz ◽  
Miguel Gallegos ◽  
Julia Contreras-García ◽  
Ángel Martín Pendás

The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown that inductive and mesomeric effects can be recognized from the decay mode of the aromatic valence bond basin populations with the distance to the substituent, and that the fluctuation of the population of adjacent bonds holds also regioselectivity information. With this, the kinetic energy of the electrons in these aromatic basins, as well as their mutual exchange-correlation energies are proposed as suitable energetic indices containing relevant information about substituent effects. We suggest that these descriptors could be used to build future reactive force fields.


ChemInform ◽  
2010 ◽  
Vol 23 (38) ◽  
pp. no-no
Author(s):  
F. M. BICKELHAUPT ◽  
N. M. M. NIBBERING ◽  
E. M. VAN WEZENBEEK ◽  
E. J. BAERENDS

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