A practical and efficient method to calculate AIM localization and delocalization indices at post‐HF levels of theory

The generalization to arbitrary molecular geometries of the energetic partitioning provided by the atomic virial theorem of the quantum theory of atoms in molecules (QTAIM) leads to an exact and chemically intuitive energy partitioning scheme, the interacting quantum atoms (IQA) approach, that depends on the availability of second-order reduced density matrices (2-RDMs). This work explores the performance of this approach in particular and of the QTAIM in general with approximate 2-RDMs obtained from the density matrix functional theory (DMFT), which rests on the natural expansion (natural orbitals and their corresponding occupation numbers) of the first-order reduced density matrix (1-RDM). A number of these functionals have been implemented in the promolden code and used to perform QTAIM and IQA analyses on several representative molecules and model chemical reactions. Total energies, covalent intra- and interbasin exchange-correlation interactions, as well as localization and delocalization indices have been determined with these functionals from 1-RDMs obtained at different levels of theory. Results are compared to the values computed from the exact 2-RDMs, whenever possible.

show abstract

“…37,38 As our work shows, the accuracy of these indices may not be good enough in strong covalent interactions.…”

Section: Discussionmentioning

confidence: 89%

Performance of the Density Matrix Functional Theory in the Quantum Theory of Atoms in Molecules

et al. 2011

View full text Add to dashboard Cite

show abstract

“…The localization and delocalization indices can be calculated from the atomic overlap matrices using readily available software such as AIMDELOC [44] or LI-DICALC [45,46].…”

Section: Electron Delocalization Between Bonded Atoms: a Direct Measumentioning

confidence: 99%

“…In this manner the summarized results can be further imported to a spreadsheet or a plotting program. Integration files -which contain the atomic overlap matrices -can be subsequently analyzed by software such as AIMDELOC [44] or LI-DICALC [45,46] to obtain the localization and delocalization indices.…”

Section: Steps Of a Typical Qtaim Calculationmentioning

confidence: 99%

An Introduction to the Quantum Theory of Atoms in Molecules

Matta

Boyd

2007

The Quantum Theory of Atoms in Molecules

483

599

View full text Add to dashboard Cite

“…In this manner, localization and delocalization indices lðAÞ and dðA; BÞ, respectively, are defined by [5]:…”

Section: The Pair-densitymentioning

confidence: 99%

Applications of the Quantum Theory of Atoms in Molecules in Organic Chemistry – Charge Distribution, Conformational Analysis and Molecular Interactions

Hernández‐Trujillo¹,

Cortés‐Guzmán²,

Cuevas³

2007

The Quantum Theory of Atoms in Molecules

View full text Add to dashboard Cite

A practical and efficient method to calculate AIM localization and delocalization indices at post‐HF levels of theory

Cited by 76 publications

References 40 publications

Performance of the Density Matrix Functional Theory in the Quantum Theory of Atoms in Molecules

Performance of the Density Matrix Functional Theory in the Quantum Theory of Atoms in Molecules

An Introduction to the Quantum Theory of Atoms in Molecules

Applications of the Quantum Theory of Atoms in Molecules in Organic Chemistry – Charge Distribution, Conformational Analysis and Molecular Interactions

Contact Info

Product

Resources

About