Challenging the electrostatic σ-hole picture of halogen bonding using minimal models and the interacting quantum atoms approach

Standard

Challenging the electrostatic σ-hole picture of halogen bonding using minimal models and the interacting quantum atoms approach. / Jiménez-Grávalos, Fernando; Gallegos, Miguel; Martín Pendás, Ángel; Novikov, Alexander S.

In: Journal of Computational Chemistry, Vol. 42, No. 10, 15.04.2021, p. 676-687.

Research output: Contribution to journal › Article › peer-review

Author

Jiménez-Grávalos, Fernando ; Gallegos, Miguel ; Martín Pendás, Ángel ; Novikov, Alexander S. / Challenging the electrostatic σ-hole picture of halogen bonding using minimal models and the interacting quantum atoms approach. In: Journal of Computational Chemistry. 2021 ; Vol. 42, No. 10. pp. 676-687.

BibTeX

@article{4bbe5ef7899e43518c920c85a2370fdd,

title = "Challenging the electrostatic σ-hole picture of halogen bonding using minimal models and the interacting quantum atoms approach",

abstract = "Among the different noncovalent interactions, halogen bonds have captured wide attention in the last years. Their stability has been rationalized in electrostatic terms by appealing to the σ-hole concept, a charge-depleted region that is able to interact favorably with electron rich moieties. This interpretation has been questioned, and in this work a set of anionic halogen model systems are used to shed some light on this issue. We use the interacting quantum atoms method, which provides an orbital invariant energy decomposition in which pure electrostatic terms are well isolated, and we complement our insights with the analysis of electrostatic potentials (ESPs) as well as with traditional descriptors of charge accumulation like the Laplacian of the electron density. The total electrostatic interaction between the interacting species is surprisingly destabilizing in many of the systems examined, demonstrating that although σ-holes might be qualitatively helpful, much care has to be taken in ascribing the stability of these systems to electrostatics. It is clearly shown that electron delocalization is essential to understand the stability of the complexes. The evolution of atomic charges as the aggregates forms reveals a charge transfer picture in which the central, σ-hole bearing halogen acts as a mere spectator. These systems may then be not far from engaging in a classical 3c-4e interaction. Since the presence of a σ-hole as characterized by the ESP mapped on a suitable molecular envelope isosurface does not guarantee attractive electrostatic interactions, we encourage to employ a wider perspective that takes into account the full charge distribution.",

author = "Fernando Jim{\'e}nez-Gr{\'a}valos and Miguel Gallegos and {Mart{\'i}n Pend{\'a}s}, {\'A}ngel and Novikov, {Alexander S.}",

year = "2021",

month = apr,

day = "15",

doi = "10.1002/jcc.26488",

language = "English",

volume = "42",

pages = "676--687",

journal = "Journal of Computational Chemistry",

issn = "0192-8651",

publisher = "Wiley-Blackwell",

number = "10",

}

RIS

TY - JOUR

T1 - Challenging the electrostatic σ-hole picture of halogen bonding using minimal models and the interacting quantum atoms approach

AU - Jiménez-Grávalos, Fernando

AU - Gallegos, Miguel

AU - Martín Pendás, Ángel

AU - Novikov, Alexander S.

PY - 2021/4/15

Y1 - 2021/4/15

N2 - Among the different noncovalent interactions, halogen bonds have captured wide attention in the last years. Their stability has been rationalized in electrostatic terms by appealing to the σ-hole concept, a charge-depleted region that is able to interact favorably with electron rich moieties. This interpretation has been questioned, and in this work a set of anionic halogen model systems are used to shed some light on this issue. We use the interacting quantum atoms method, which provides an orbital invariant energy decomposition in which pure electrostatic terms are well isolated, and we complement our insights with the analysis of electrostatic potentials (ESPs) as well as with traditional descriptors of charge accumulation like the Laplacian of the electron density. The total electrostatic interaction between the interacting species is surprisingly destabilizing in many of the systems examined, demonstrating that although σ-holes might be qualitatively helpful, much care has to be taken in ascribing the stability of these systems to electrostatics. It is clearly shown that electron delocalization is essential to understand the stability of the complexes. The evolution of atomic charges as the aggregates forms reveals a charge transfer picture in which the central, σ-hole bearing halogen acts as a mere spectator. These systems may then be not far from engaging in a classical 3c-4e interaction. Since the presence of a σ-hole as characterized by the ESP mapped on a suitable molecular envelope isosurface does not guarantee attractive electrostatic interactions, we encourage to employ a wider perspective that takes into account the full charge distribution.

AB - Among the different noncovalent interactions, halogen bonds have captured wide attention in the last years. Their stability has been rationalized in electrostatic terms by appealing to the σ-hole concept, a charge-depleted region that is able to interact favorably with electron rich moieties. This interpretation has been questioned, and in this work a set of anionic halogen model systems are used to shed some light on this issue. We use the interacting quantum atoms method, which provides an orbital invariant energy decomposition in which pure electrostatic terms are well isolated, and we complement our insights with the analysis of electrostatic potentials (ESPs) as well as with traditional descriptors of charge accumulation like the Laplacian of the electron density. The total electrostatic interaction between the interacting species is surprisingly destabilizing in many of the systems examined, demonstrating that although σ-holes might be qualitatively helpful, much care has to be taken in ascribing the stability of these systems to electrostatics. It is clearly shown that electron delocalization is essential to understand the stability of the complexes. The evolution of atomic charges as the aggregates forms reveals a charge transfer picture in which the central, σ-hole bearing halogen acts as a mere spectator. These systems may then be not far from engaging in a classical 3c-4e interaction. Since the presence of a σ-hole as characterized by the ESP mapped on a suitable molecular envelope isosurface does not guarantee attractive electrostatic interactions, we encourage to employ a wider perspective that takes into account the full charge distribution.

UR - http://www.scopus.com/inward/record.url?scp=85100814733&partnerID=8YFLogxK

U2 - 10.1002/jcc.26488

DO - 10.1002/jcc.26488

M3 - Article

C2 - 33566376

AN - SCOPUS:85100814733

VL - 42

SP - 676

EP - 687

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 10

ER -

ID: 77246641