Current trends in the development of A. M. Butlerov’s theory of chemical structure

Minkin, V. I.

doi:10.1007/s11172-012-0174-7

Cited by 15 publications

(9 citation statements)

References 87 publications

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“…At the next stage during the NEO-HF calculations of each species in both series in addition to the usual linear optimization of the SCF coefficients of the hybrid basis set, 23 the inter-nuclear distance of the clamped nuclei and the centers and exponents of the mobile functions were all optimized with a non-linear non-gradient optimizer added externally to the NEO code. At the final stage of ab initio calculations the gradient of energy was computed explicitly to ensure the precision of the external optimizer; the root mean square of forces operative on the nuclei and the PCP was always less than 5 10 − Hartree/Bohr in all considered species while the maximum force was always less than 4 10 − Hartree/Bohr. The designed procedure is a combination of the orthodox NEO-HF, which is usually used with fixed-center basis sets with pre-defined exponents, 23 and the fully variational multi-component Hartree-Fock method that optimizes all variables of a basis set.…”

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

confidence: 99%

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

confidence: 99%

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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“…However, the use of Equation (8) most understandable by chemists is based on counting inequivalent graph vertices and graph edges corresponding to quintessential chemical concepts, atoms, and chemical bonds. Herewith, the application of Equation (8) to the vertices seems stricter as the atoms in the molecules are uniquely identified [33]. In contrast, a chemical bond is a vague concept because its strict criteria are absent [33], and when selecting chemical bonds in the molecule, chemists are guided by intuition (in most cases, such an 'intuitive approach ' works well but there are debatable examples, especially related to coordination compounds, endohedral complexes, molecules with multicenter chemical bonds [33][34][35][36]).…”

Section: Discrete Information Entropy Approach: Quantifying Molecules As a Setmentioning

confidence: 99%

Information Entropy in Chemistry: An Overview

Sabirov

Shepelevich

2021

Entropy

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Basic applications of the information entropy concept to chemical objects are reviewed. These applications deal with quantifying chemical and electronic structures of molecules, signal processing, structural studies on crystals, and molecular ensembles. Recent advances in the mentioned areas make information entropy a central concept in interdisciplinary studies on digitalizing chemical reactions, chemico-information synthesis, crystal engineering, as well as digitally rethinking basic notions of structural chemistry in terms of informatics.

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“…In doing this, he was also one of the pioneers of representing organic molecules with a two-dimensional structure connected by lines, representing the bonds or valences [142]. As Butlerov wrote, "Starting from the assumption that each chemical atom possesses only a definite and limited amount of chemical force (affinity) with which it takes part in forming a compound, I might call this chemical arrangement, or the type and manner of the mutual binding of the atoms in a compound substance, by the name of chemical structure" [143][144][145]. This can be seen as the beginning of the structural theory of organic chemistry [146].…”

Section: Organic Chemistry and Structure-the Bond Reigns Supremementioning

confidence: 99%

Chemical Bonding: The Journey from Miniature Hooks to Density Functional Theory

Constable

Housecroft

2020

Molecules

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Our modern understanding of chemistry is predicated upon bonding interactions between atoms and ions resulting in the assembly of all of the forms of matter that we encounter in our daily life. It was not always so. This review article traces the development of our understanding of bonding from prehistory, through the debates in the 19th century C.E. bearing on valence, to modern quantum chemical models and beyond.

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Current trends in the development of A. M. Butlerov’s theory of chemical structure

Cited by 15 publications

References 87 publications

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

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

Information Entropy in Chemistry: An Overview

Chemical Bonding: The Journey from Miniature Hooks to Density Functional Theory

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