Electron Communications and Chemical Bonds

Nalewajski, Roman F.

doi:10.1007/978-981-10-5651-2_14

Cited by 12 publications

(24 citation statements)

References 93 publications

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“…It has been argued elsewhere that elements of the CBO matrix also generate amplitudes of electronic communications between molecular AO "events". [1,[36][37][38][49][50][51][52][53][54][55][56][57][58][59] This observation adds a new angle to interpreting the average-information expression as the communication-weighted (dimentionless) kinetic energy of the system electrons [83] .…”

Section: Resultant Gradient-information and Kinetic Energy Of Electronsmentioning

confidence: 99%

“…Information principles have been explored [5][6][7][8][40][41][42][43][44][45] and density pieces attributed toAtoms-in-Molecules(AIM) have been approached, [36][37][38][39][43][44][45][46][47] providing the information basis for the intuitive (stockholder) division of Hirshfeld [48] . Patterns of chemical bonds in molecules have been extracted from electronic orbital communications, [1,[36][37][38][49][50][51][52][53][54][55][56][57][58][59] and entropy/information densities have been explored. [1, 36-38, 60, 61] The nonadditive Fisher information [1, 36-38, 62, 63] has been linked to the Electron Localization Function (ELF) [64][65][66] of modern DFT.…”

Section: Introductionmentioning

confidence: 99%

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Resultant gradient information, kinetic energy and molecular virial theorem

Nalewajski

2019

Chem Rep

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Resultant gradient-information is introduced and applied to problems in chemical reactivity theory. This local measure of the structural information contained in (complex) wavefunctions of electronic states is related to the system overall kinetic energy combining the modulus (probability) and phase (current) contributions. The grand-ensemble representation of thermodynamic equilibria in open systems demonstrates the physical equivalence of the variational energetic and information principles. It is used and to relate the populational derivatives of ensemble-average functionals in both these representations, which represent reactivity criteria for diagnosing the charge-transfer (CT) phenomena. Their equivalence is demonstrated by using the in situ potential and hardness descriptors to predict the direction and optimum amount of CT. The virial theorem is generalized into thermodynamic quantities and used to extract the kinetic energy component from qualitative energy profiles in the bond-formation and (exo/endo)-ergic reactions. The role of electronic kinetic energy in such chemical processes is reexamined, the virial theorem implications for the Hammond postulate of reactivity theory are explored, and variations of the structural-information in chemical processes are addressed. The maximum thermodynamic information rule is formulated and "production" of the gradient-information in chemical reactions is addressed. The Hammond postulate is shown to be indexed by the geometric derivative of resultant gradient-information at transition-state complex.

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Section: Resultant Gradient-information and Kinetic Energy Of Electronsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Resultant gradient information, kinetic energy and molecular virial theorem

Nalewajski

2019

Chem Rep

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“…The IT approach has proven its utility in a variety of molecular scenarios, e.g., [39–42]. In this analysis we examined mutual relations between densities of the classical and nonclassical components of the resultant information/entropy measures, combining the probability contributions of Fisher or Shannon and their associated phase/current supplements.…”

Section: Discussionmentioning

confidence: 99%

“…The IT principles using the resultant quantum descriptors of the entropy/information content in electronic states have also been used to determine the phase and information equilibria in molecules and their constituent parts [12–18]. The phase aspect of molecular states is also vital for the quantum (amplitude) communications between atoms in molecules [2–5, 42], which determine entropic descriptors of the chemical bond multiplicities and their covalent/ionic composition.…”

Section: Discussionmentioning

confidence: 99%

Information equilibria, subsystem entanglement, and dynamics of the overall entropic descriptors of molecular electronic structure

Nalewajski

2018

J Mol Model

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Overall descriptors of the information (determinicity) and entropy (uncertainty) content of complex molecular states are reexamined. These resultant concepts combine the classical (probability) contributions of Fisher and Shannon, and the relevant nonclassical supplements due to the state phase/current. The information-theoretic principles determining equilibria in molecules and their fragments are explored and the nonadditive part of the global entropy is advocated as a descriptor of the classical index of the quantum entanglement of molecular subsystems. Affinities associated with the probability and phase fluxes are identified and the criterion of vanishing overall information-source is shown to identify the system stationary electronic states. The production of resultant density of the gradient-information is expressed in terms of the conjugate affinities (forces, perturbations) and fluxes (currents, responses). The Schrödinger dynamics of probability and phase components of molecular electronic states is used to determine the temporal evolution of the overall gradient information and complex entropy. The global sources of the resultant information/entropy descriptors are shown to be of purely nonclassical origin, thus identically vanishing in real electronic states, e.g., the nondegenerate ground state of a molecule.

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“…The familiar information/entropy measures of Fisher [3,4] and Shannon [5,6] only reflect the state information/entropy content due to the probability distribution, thus failing to distinguish states exhibiting the same electron density but different current compositions. The recently introduced resultant IT descriptors [2,[16][17][18][19][20][21][22] combine these classical contributions with their respective nonclassical supplements due to the state phase/current. The densities of the nonclassical information/entropy terms exhibit the same mutual relations as their classical analogs and they introduce the nonvanishing source terms into their respective continuity relations [2].…”

Section: Introductionmentioning

confidence: 99%

Solid State Coordination Chemistry and Supramolecular Assemblies of (II)/Benzilato/2,2'Dipyridylamine Systems

Carballo¹,

Covelo²,

Paz³

2017

Struct Chem Crystallogr Commun

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The dynamics of probability (modulus) and phase (current) components of general electronic states is used to determine the temporal evolution of the overall descriptors of the information (determinicity) and entropy (indeterminicity) content of complex molecular states. These resultant information-theoretic concepts combine the classical (probability) contributions of Fisher and Shannon, and the corresponding nonclassical supplements due to the state phase/current. The total time derivatives of such overall measures of the gradient information and complex entropy are determined from Schrödinger's equation using the chainrule transformations. These overall productions of the gradient information and complex entropy are shown to be of a purely nonclassical origin, thus identically vanishing in real electronic states, e.g., the nondegenerate ground state of a molecule.

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Electron Communications and Chemical Bonds

Cited by 12 publications

References 93 publications

Resultant gradient information, kinetic energy and molecular virial theorem

Resultant gradient information, kinetic energy and molecular virial theorem

Information equilibria, subsystem entanglement, and dynamics of the overall entropic descriptors of molecular electronic structure

Solid State Coordination Chemistry and Supramolecular Assemblies of (II)/Benzilato/2,2'Dipyridylamine Systems

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