Molecular QTAIM Topology Is Sensitive to Relativistic Corrections
James S. M. Anderson,James S. M. Anderson,Juan I. Rodríguez,Paul W. Ayers,Daniel E. Trujillo-González,Andreas W. Götz,Jochen Autschbach,Fray de Landa Castillo-Alvarado,Koichi Yamashita +8 more
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TL;DR: The sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization is established, consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied.
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Abstract: The topology of the molecular electron density of benzene dithiol gold cluster complex Au4 -S-C6 H4 -S'-Au'4 changed when relativistic corrections were made and the structure was close to a minimum of the Born-Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.
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Citations
A Topological Data Analysis Perspective on Non-Covalent Interactions in Relativistic Calculations
TL;DR: In this article, the effects of relativistic effects on the bonding of the Au4S-C6H4-S'-Au'4 molecule were investigated, and it was shown from their low persistence values (which decrease with increased basis set size) these features are not significant.
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A Topological Data Analysis perspective on noncovalent interactions in relativistic calculations
TL;DR: In this paper, the effects of relativistic effects on the bonding of the Au4−S−C6H4•S′•Au′4 molecule were investigated. But the results showed that relativism-induced noncovalent interactions between gold and hydrogen atoms are not significant.
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Quantum chemical topology at the spin-orbit configuration interaction level: Application to astatine compounds.
Cecilia Gomez Pech,Pi A. B. Haase,Dumitru-Claudiu Sergentu,Dumitru-Claudiu Sergentu,Anastasia Borschevsky,Julien Pilmé,Nicolas Galland,Rémi Maurice +7 more
TL;DR: A methodology that allows the investigation of the consequences of the spin–orbit coupling by means of the QTAIM and ELF topological analyses performed on top of relativistic and multiconfigurational wave functions and can be applied to the ground and/or excited states of any compound, with controlled validity.
New insights in chemical reactivity from quantum chemical topology.
TL;DR: Based on the quantum chemical topology of the modified electron localization function ELFx, an efficient and robust mechanistic methodology designed to identify the favorable reaction pathway between two reactants is proposed in this paper.
Relativistic Hirshfeld atom refinement of an organo-gold(I) compound
Sylwia Pawlędzio,Maura Malinska,Magdalena Woińska,Jakub Wojciechowski,Lorraine A. Malaspina,Florian Kleemiss,Simon Grabowsky,Krzysztof Woźniak +7 more
TL;DR: In this paper, the influence of relativistic effects on statistical parameters, geometries and electron density properties was analyzed and compared with electron correlation and anharmonic atomic motions.
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References
Generalized Gradient Approximation Made Simple
TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
94.9K
Self-Consistent Equations Including Exchange and Correlation Effects
Walter Kohn,L. J. Sham +1 more
TL;DR: In this paper, the Hartree and Hartree-Fock equations are applied to a uniform electron gas, where the exchange and correlation portions of the chemical potential of the gas are used as additional effective potentials.
Density-functional exchange-energy approximation with correct asymptotic behavior.
TL;DR: This work reports a gradient-corrected exchange-energy functional, containing only one parameter, that fits the exact Hartree-Fock exchange energies of a wide variety of atomic systems with remarkable accuracy, surpassing the performance of previous functionals containing two parameters or more.
Inhomogeneous Electron Gas
P. C. Hohenberg,Walter Kohn +1 more
TL;DR: In this article, the ground state of an interacting electron gas in an external potential was investigated and it was proved that there exists a universal functional of the density, called F[n(mathrm{r})], independent of the potential of the electron gas.
49.6K