Nearsightedness of Electronic Matter As Seen by a Physicist and a Chemist

Bader, R. F. W.

doi:10.1021/jp806282j

Cited by 45 publications

(35 citation statements)

References 83 publications

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“…This observation hints that in all the considered species, hydrogen isotopes' distributions are "confined" to the interior of hydrogen basins, not "leaking" on or beyond the inter-atomic surfaces (vide infra). The fact that most sensitive topological "probes" for isotope substitution, and concomitant induced perturbation in electron's distribution, is the topological indices of the C-X associated LCPs conforms to the idea of the nearsightedness of electronic matter advocated by Bader [26,27].…”

Section: The Topological Analysissupporting

confidence: 55%

Topological and AIM analyses beyond the Born–Oppenheimer paradigm: New opportunities

Goli

Shahbazian

2015

Computational and Theoretical Chemistry

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The multi-component quantum theory of atoms in molecules (MC-QTAIM) analysis is done on methane, ethylene, acetylene and benzene as selected basic hydrocarbons. This is the first report on applying the MC-QTAIM analysis on polyatomic species. In order to perform the MC-QTAIM analysis, at first step the nuclear-electronic orbital method at Hartree-Fock level (NEO-HF) is used as a non-Born-Oppenheimer (nBO) ab initio computational procedure assuming both electrons and protons as quantum waves while carbon nuclei as point charges in these systems. The ab initio calculations proceed substituting all the protons of each species first with deuterons and then tritons. At the next step, the derived nBO wavefunctions are used for the "atoms in molecules" (AIM) analysis.The results of topological analysis and integration of atomic properties demonstrate that the MC-QTAIM is capable of deciphering the underlying AIM structure of all the considered species. Also, the results of the analysis for each isotopic composition are distinct and the fingerprint of the mass difference of hydrogen isotopes is clearly seen in both topological and AIM analyses. This isotopic distinction is quite unique in the MC-QTAIM and not recovered by the orthodox QTAIM that treats nuclei as clamped particles. The results of the analysis also demonstrate that each quantum nucleus that forms an atomic basin resides within its own basin. The confinement of quantum nuclei within a single basin is used to simplify the basic equations of the MC-QTAIM paving the way for future theoretical studies. KeywordsClamped nucleus model; topological analysis; quantum theory of atoms in molecules; nonBorn-Oppenheimer; multi-component systems 2

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Section: The Topological Analysissupporting

confidence: 55%

Topological and AIM analyses beyond the Born–Oppenheimer paradigm: New opportunities

Goli

Shahbazian

2015

Computational and Theoretical Chemistry

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“…It is evident from Tables S1 and S2 that in both series of species the topological indices of (3, -3) CPs at the clamped nuclei and the (3, -1) CP in between are almost constant and relatively insensitive to the mass variation of the PCP. As is also stressed recently, 70 this is a manifestation of the principle of the nearsightedness of the electronic matter, 86,87 which roughly states that a perturbation induced by a variation on a specific site of a molecule damps beyond the region of perturbation when considering the electronic density as well as the property densities. Manifestly, the mass variation of the PCP, which acts similar to a perturbation, is best manifested on the topological indices computed at the PCP associated (3, -3) CP as well as the (3, -1) CP at the boundary of the X basin and its neighboring basin.…”

Section: A Brief Survey On the Computational Procedures And The Mass mentioning

confidence: 89%

Hidden aspects of the Structural theory of chemistry: MC-QTAIM analysis reveals “alchemical” transformation from a triatomic to a diatomic structure

Goli

Shahbazian

2015

Phys. Chem. Chem. Phys.

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The Structural theory of chemistry introduces chemical/molecular structure as a combination of relative arrangement and bonding patterns of atoms in a molecule. Nowadays, the structure of atoms in molecules is derived from the topological analysis of the quantum theory of atoms in molecules (QTAIM). In this context, a molecular structure is varied by large geometrical variations and concomitant reorganization of electronic structure that usually take place in chemical reactions or under extreme hydrostatic pressure. In this report, a new mode of structural variation is introduced within the context of the newly proposed multi-component QTAIM (MC-QTAIM) that originates from the mass variation of nuclei. Accordingly, XCN and CNX series of species are introduced where X stands for a quantum particle with a unit of positive charge and a variable mass that is varied in discrete steps between the mass of a proton and a positron. Ab initio non-Born-Oppenheimer (non-BO) calculations are done on both series of species and the resulting non-BO wavefunctions are used for the MC-QTAIM analysis, revealing a triatomic structure for the proton mass and a diatomic structure for the positron mass. In both series of species, a critical mass between that of proton and positron mass is discovered where the transition from triatomic to diatomic structure takes place. This abrupt structural transformation has a topological nature resembling the usual phase transitions in thermodynamics. The discovered mass-induced structural transformation is a hidden aspect of the Structural theory which is revealed only beyond the BO paradigm, when nuclei are treated as quantum waves instead of clamped point charges.

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“…It is the transferable nature of the viral field that is responsible for the concept of a functional group in chemistry and for the theorem that the density of an atom in a molecule determines all of its properties. 55 The quantum definition of the energy of an atom in a molecule must include its interaction with the entire system. A bond energy is no more precisely defined than is a bond, but its need is obviated by QTAIM, which offers among other possible analyses of the interactions between atoms, 20,45,56 the definition of the contribution to the energy of formation arising from the formation of an interatomic surface and its associated bond path.…”

Section: There Is No Curvature Of the Potential Energy Surface Corresmentioning

confidence: 99%

Bond Paths Are Not Chemical Bonds

2009

Self Cite

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This account takes to task papers that criticize the definition of a bond path as a criterion for the bonding between the atoms it links by mistakenly identifying it with a chemical bond. It is argued that the notion of a chemical bond is too restrictive to account for the physics underlying the broad spectrum of interactions between atoms and molecules that determine the properties of matter. A bond path on the other hand, as well as being accessible to experimental verification and subject to the theorems of quantum mechanics, is applicable to any and all of the interactions that account for the properties of matter. It is shown that one may define a bond path operator as a Dirac obserVable, making the bond path the measurable expectation Value of a quantum mechanical operator. Particular attention is given to van der Waals interactions that traditionally are assumed to represent attractive interactions that are distinct from chemical bonding. They are assumed by some to act in concert with Pauli repulsions to account for the existence of condensed states of molecules. It is such dichotomies of interpretation that are resolved by the experimental detection of bond paths and the delineation of their properties in molecular crystals. Specific criticisms of the stabilization afforded by the presence of bond paths derived from spectroscopic measurements performed on dideuteriophenanthrene are shown to be physically unsound. The concept of a bond path as a "bridge of density" linking bonded atoms was introduced by London in 1928 following the definition of the electron density by Schrödinger in 1926. These papers marked the beginning of the theory of atoms in molecules linked by bond paths.

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Nearsightedness of Electronic Matter As Seen by a Physicist and a Chemist

Cited by 45 publications

References 83 publications

Topological and AIM analyses beyond the Born–Oppenheimer paradigm: New opportunities

Topological and AIM analyses beyond the Born–Oppenheimer paradigm: New opportunities

Hidden aspects of the Structural theory of chemistry: MC-QTAIM analysis reveals “alchemical” transformation from a triatomic to a diatomic structure

Bond Paths Are Not Chemical Bonds

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