Correlations between Density-Based Bond Orders and Orbital-Based Bond Energies for Chemical Bonding Analysis

Roderigh Y. Rohling, Ionut C. Tranca, Emiel J.M. Hensen (Corresponding author), Evgeny A. Pidko (Corresponding author)

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Quantum chemistry-based codes and methods provide valuable computational tools to estimate reaction energetics and elucidate reaction mechanisms. Electronic structure methods allow directly studying the chemical transformations in molecular systems involving breaking and making of chemical bonds and the associated changes in the electronic structure. The link between the electronic structure and chemical bonding can be provided through the crystal orbital Hamilton population (COHP) analysis that allows quantifying the bond strength by computing Hamilton-weighted populations of localized atomic orbitals. Another important parameter reflecting the nature and strength of a chemical bond is the bond order that can be assessed by the density derived electrostatic and chemical (DDEC6) method which relies on an electron and spin density-partitioning scheme. Herein, we describe a linear correlation that can be established between the DDEC6-derived bond orders and the bond strengths computed with the COHP formalism. We demonstrate that within defined boundaries, the COHP-derived bond strengths can be consistently compared among each other and linked to the DDEC6-derived bond orders independent of the used model. The validity of these correlations and the effective model independence of the electronic descriptors are demonstrated for a variety of gas-phase chemical systems, featuring different types of chemical bonds. Furthermore, the applicability of the derived correlations to the description of complex reaction paths in periodic systems is demonstrated by considering the zeolite-catalyzed Diels-Alder cycloaddition reaction between 2,5-dimethylfuran and ethylene. ©

Originele taal-2Engels
Pagina's (van-tot)2843-2854
Aantal pagina's12
TijdschriftJournal of Physical Chemistry C
Volume123
Nummer van het tijdschrift5
DOI's
StatusGepubliceerd - 7 feb 2019

Vingerafdruk

Chemical bonds
Electronic structure
chemical bonds
orbitals
Crystals
electronic structure
Zeolites
Quantum chemistry
Cycloaddition
Time varying systems
crystals
energy
Electrostatics
Ethylene
quantum chemistry
cycloaddition
Gases
electron spin
ethylene
Electrons

Citeer dit

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abstract = "Quantum chemistry-based codes and methods provide valuable computational tools to estimate reaction energetics and elucidate reaction mechanisms. Electronic structure methods allow directly studying the chemical transformations in molecular systems involving breaking and making of chemical bonds and the associated changes in the electronic structure. The link between the electronic structure and chemical bonding can be provided through the crystal orbital Hamilton population (COHP) analysis that allows quantifying the bond strength by computing Hamilton-weighted populations of localized atomic orbitals. Another important parameter reflecting the nature and strength of a chemical bond is the bond order that can be assessed by the density derived electrostatic and chemical (DDEC6) method which relies on an electron and spin density-partitioning scheme. Herein, we describe a linear correlation that can be established between the DDEC6-derived bond orders and the bond strengths computed with the COHP formalism. We demonstrate that within defined boundaries, the COHP-derived bond strengths can be consistently compared among each other and linked to the DDEC6-derived bond orders independent of the used model. The validity of these correlations and the effective model independence of the electronic descriptors are demonstrated for a variety of gas-phase chemical systems, featuring different types of chemical bonds. Furthermore, the applicability of the derived correlations to the description of complex reaction paths in periodic systems is demonstrated by considering the zeolite-catalyzed Diels-Alder cycloaddition reaction between 2,5-dimethylfuran and ethylene. {\circledC}",
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Correlations between Density-Based Bond Orders and Orbital-Based Bond Energies for Chemical Bonding Analysis. / Rohling, Roderigh Y.; Tranca, Ionut C.; Hensen, Emiel J.M. (Corresponding author); Pidko, Evgeny A. (Corresponding author).

In: Journal of Physical Chemistry C, Vol. 123, Nr. 5, 07.02.2019, blz. 2843-2854.

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

TY - JOUR

T1 - Correlations between Density-Based Bond Orders and Orbital-Based Bond Energies for Chemical Bonding Analysis

AU - Rohling, Roderigh Y.

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