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The Source Function Descriptor as a Tool to Extract Chemical Information from Theoretical and Experimental Electron Densities

  • Carlo GattiEmail author
Part of the Structure and Bonding book series (STRUCTURE, volume 147)

Abstract

This chapter deals with the source function (SF) descriptor, originally put forth by Bader and Gatti back in 1998. After a brief review on how this descriptor is defined and what it physically represents, the various forms through which the SF may be analyzed are presented in some detail. The relationships between atomic SF contributions and chemical bond nature are analyzed in some prototypical cases, and the capability of the SF to neatly reveal π-electron conjugation directly from the electron distribution and independently from any MO scheme or decomposition is introduced. Applications of the SF to chemistry from the literature are reviewed and critically discussed, including the use of the SF to assess chemical transferability or to describe chemical bonding in challenging situations, like for instance the short-strong hydrogen bonds in π-conjugated frameworks or the metal–metal and metal–ligand interactions in the organometallic complexes. Comparison with the insight obtained from other bond topological descriptors is given, emphasizing the special role the SF has of being directly derivable from experimental electron density distributions and to so provide an ideal tool to compare experiment and theory. The robustness of the SF descriptor against changes in the models used to derive electron densities from theory of experiment is detailed. First results on using the SF to define an unambiguous full population analysis are outlined. The possible ways of further decomposing the atomic SF in chemically meaningful additive pieces, such as core and valence atomic contributions, are analyzed in view of their potential insight and degree of arbitrariness.

Keywords

Chemical transferability Electron conjugation Local and nonlocal bonding descriptors Metal–metal and metal–ligand bonds Population analysis Short-strong hydrogen bonds Source function and chemical bonding Theoretical and experimental electron densities 

Abbreviations

±CAHB

Positively(negatively) charge-assisted hydrogen bond

Bcp

Bond critical point (in RFW Bader’s theory)

BP

Bond path (in RFW Bader’s theory)

Bza

Benzoylacetone

CC

Charge concentration

Cp

Critical point (in RFW Bader’s theory)

DAFH

Domain-averaged Fermi hole

DFT

Density functional theory

ELF

Electron localization function

HB

Hydrogen bond

HF

Hartree–Fock

HS

Hirshfeld surfaces (M Spackman’s definition)

IAM

Independent atom model

IAS

Interatomic surface (in RFW Bader’s theory)

ICP

Interchanged population

IHB

Isolated hydrogen bond

IP

Ignored population

IQA

Interacting quantum atoms

LBHB

Low-barrier hydrogen bond

LS

Local source function

MM

Multipole model

MMED

Multipole model experimental density

MMPD

Multipole-modeled primary density

Mp

Midpoint (along an internuclear axis)

MPA

Mulliken’s population analysis

NBO

Natural bond order

Nma

Nitromalonamide

PAHB

Polarization-assisted hydrogen bond

PD

Primary density (usually from ab initio computations)

QTAIM

Quantum theory of atoms in molecules (RFW Bader’s theory)

RAHB

Resonance-assisted hydrogen bond

Rcp

Ring critical point (in RFW Bader’s theory)

Rp

Reference point

SF

Source function

SSHB

Short-strong hydrogen bond

TMM

Trimethylenemethane complex

VSCC

Valence shell charge concentration (RFW Bader’s theory)

Notes

Acknowledgments

I am deeply indepted to and warmly thank Richard Bader for his fundamental contribution to the seminal work on the Source Function. I also thank Luca Bertini, Fausto Cargnoni, Davide Lasi, and Leonardo Lo Presti for their precious collaboration in developing and applying the SF. I thank the Danish National Research Foundation for partial funding of this work through the Center for Materials Crystallography (CMC).

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© Springer-Verlag Berlin Heidelberg 2011

Authors and Affiliations

  1. 1.Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) e Dipartimento di Chimica Fisica ed ElettrochimicaUniversità di MilanoMilanoItaly
  2. 2.Center for Materials CrystallographyAarhus UniversityAarhus CDenmark

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