Natural bond critical point analysis: Quantitative relationships between natural bond orbital‐based and QTAIM‐based topological descriptors of chemical bonding

Weinhold, Frank

doi:10.1002/jcc.23057

Cited by 94 publications

(103 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…From the sum of two such atom densities ρ A (r), ρ B (r), one can also calculate the corresponding NBO-based 'natural bond critical point' (NBCP) position r NBCP and density ρ NBCP , for direct comparison with QTAIM-based r BCP and density ρ BCP [36]. as 'diagonal elements' of the associated integral operator) from the same 1-RDM that is provided as input to NBO.…”

Section: Nbo Vs Qtaim Methodsmentioning

confidence: 99%

What is NBO analysis and how is it useful?

Weinhold

Landis

Glendening

2016

International Reviews in Physical Chemistry

685

391

View full text Add to dashboard Cite

Natural bond orbital (NBO) analysis is one of many available options for 'translating' computational solutions of Schrödinger's wave equation into the familiar language of chemical bonding concepts. In this Review, we first address the title questions by describing characteristic features that distinguish NBO from alternative analysis methodologies (e.g. of QTAIM or EDA type) and answering criticisms that have been raised in specific chemical applications. We then address the general 'usefulness' of NBO analysis in the context of widely accepted philosophical criteria, including (i) broad consistency, both internally and with respect to known experimental data, (ii) multi-faceted predictive capacity, including numerical model predictions of specific properties, general correlative and statistical regression relationships, and 'risky' falsifiable predictions of previously unknown chemical phenomena, and (iii) general pedagogical value, promoting organisation, unification, and orderly rationalisation of chemical knowledge. Specific chemical topics chosen for discussion include controversial H⋯H 'bond lines' in bay-type hydrocarbon species; carbene ligation of coinage metals; resonance-type bonding of noble gas hydrides; NBO descriptors in Hammett-type quantitative structure-activity relationships; nature of conventional and 'anti-electrostatic' hydrogen bonding interactions; multi-centre bonding in 'aromatic' Al ð2ÀÞ 4 , Lewis-like hybridisation picture of non-VSEPR geometry and high-order multiple bonding in transition metal species; resonance origin of the '18e rule'; and localised (symmetry-independent) prediction of Jahn-Teller effects in free radical chemistry. We conclude with hints of some directions for future extensions of NBO methods.

show abstract

Section: Nbo Vs Qtaim Methodsmentioning

confidence: 99%

What is NBO analysis and how is it useful?

Weinhold

Landis

Glendening

2016

International Reviews in Physical Chemistry

685

391

View full text Add to dashboard Cite

show abstract

“…[28]. Although many regard the debate to be stale [37,38], new papers are still being published regarding the interpretation and physical nature of AILs [39][40][41][42][43][44][45][46]. NCI managed to solve one branch of QTAIM-associated problems, by showing that the absence of an AIL does not imply that electron density cannot be concentrated in the bonding region of an interaction.…”

Section: Introductionmentioning

confidence: 99%

Evaluating common QTAIM and NCI interpretations of the electron density concentration through IQA interaction energies and 1D cross-sections of the electron and deformation density distributions

Cukrowski

Lange

Adeyinka

et al. 2015

Computational and Theoretical Chemistry

View full text Add to dashboard Cite

Highlights• Classical steric clashes might have the same topological features as bonding interactions.• An AIL can be observed for highly attractive or repulsive interactions.• An AIL might be a result of either an inflow or outflow of density.• Locally accumulated density does not imply an attractive interaction or an inflow of density.• Nature of an interaction can change with molecular environment. Graphical abstract 2 AbstractNine kinds of inter-and intramolecular interactions were investigated by exploring the topology of electron density in the interatomic regions using standard protocols of QTAIM, IQA and NCI techniques as well as in-house developed cross-sections of the electron and deformation density distributions. The first four methods provide the properties of the resultant density distribution in a molecular system whereas the later illustrates the process, inflow or outflow of density from fragments to the interatomic region of an interaction on its formation in a molecular system. We used (i) the QTAIM-defined atomic interaction line, AIL (presence or absence), (ii) IQA-defined interaction energy, attractive to repulsive, (ii)  2 < 0 to  2 >0, or (iii) (r) > 0 to (r) < 0; hence, none of the topological indices used here, either separately or combined, can be used to definitely predict the (de)stabilizing nature of an interaction except highly repulsive ones for which the absence of AIL, interatomic density depletion and outflow of density on interaction formation are observed.

show abstract

“…We thus extended the analysis of the nature of the Fe–C interaction by calculating the Natural Bond Critical Points (NBCPs). 41 Based on the atom in molecules (AIM) concept, the presence of a CP on the line joining two atoms indicates a chemical bond, while the electron density at the CP measures the strength of the bond. Finally, the sign of the Laplacian of the electron density, ∇ 2 ρ ( r ), is an indication of the concentration or depletion of electron density, with ∇ 2 ρ ( r ) < 0 and >0 indicating the covalent or ionic character of the bond.…”

Section: Resultsmentioning

confidence: 99%