TY - JOUR
T1 - Toward a uniform description of hydrogen bond and halogen bond: correlations of interaction energies with various geometric, electronic and topological parameters
AU - Zou, Jian-Wei
AU - Huang, Meilan
AU - Hu, Gui-Xiang
AU - Jiang, Yong-Jun
PY - 2017/2/7
Y1 - 2017/2/7
N2 - Halogen bonds, which are specific non-covalent interactions similar to hydrogen bonds, play crucial roles in
fields as diverse as supramolecular assemblies, crystal engineering, and biological systems. A total of 108
halogen-bonded and hydrogen-bonded complexes formed by different electron acceptors and NH3,
namely, R–A/NH3 (A ¼ H, Cl, Br or I), have been investigated at the MP2(full)/aug-cc-pVDZ(-PP) level of
theory. The relationships between the interaction strengths and various geometric and electronic
structures, as well as topological properties, were established, with a particular focus on the uniformity
of these two types of interaction. The dependence of the BSSE-corrected interaction energy (DEcor) on
the interatomic distance (rA/N) appeared to be nonlinear for both halogen-bonded and hydrogenbonded
systems; the relationship between DEcor and the difference between rA/N and the sum of the
van der Waals radii (DrA/N) can be fitted to a combined quadratic regression equation. Furthermore, we
demonstrated that the linear correlations between DEcor and rb(BCP) (the electron density at bond
critical points in the A/N bond) and its Laplacian V2
rb(BCP) can be used to provide a combined
description of hydrogen bonds and halogen bonds, with correlation coefficients of 0.964 and 0.956,
respectively. The dependence of the interaction strength on the electrostatic potential corresponding to
an electron density of 0.002 a.u. along the R–A bond vector (ESP0.002), the amount of charge transferred
(QCT) and the second-order perturbation stabilization energies of n(NH3) / s*(R–A) (E(2)) were also
examined. Strong halogen-bonded complexes were found to exhibit different linear correlations from
weak halogen-bonded and hydrogen-bonded systems. Nevertheless, for the latter two types of system,
a uniform regression equation can be constructed. These relationships not only improve our
understanding of the nature of halogen bonding but also provide a feasible approach for predicting or
determining the relative strengths of hydrogen bonds and halogen bonds, in particular when both types
of non-covalent interaction coexist and compete with each other.
AB - Halogen bonds, which are specific non-covalent interactions similar to hydrogen bonds, play crucial roles in
fields as diverse as supramolecular assemblies, crystal engineering, and biological systems. A total of 108
halogen-bonded and hydrogen-bonded complexes formed by different electron acceptors and NH3,
namely, R–A/NH3 (A ¼ H, Cl, Br or I), have been investigated at the MP2(full)/aug-cc-pVDZ(-PP) level of
theory. The relationships between the interaction strengths and various geometric and electronic
structures, as well as topological properties, were established, with a particular focus on the uniformity
of these two types of interaction. The dependence of the BSSE-corrected interaction energy (DEcor) on
the interatomic distance (rA/N) appeared to be nonlinear for both halogen-bonded and hydrogenbonded
systems; the relationship between DEcor and the difference between rA/N and the sum of the
van der Waals radii (DrA/N) can be fitted to a combined quadratic regression equation. Furthermore, we
demonstrated that the linear correlations between DEcor and rb(BCP) (the electron density at bond
critical points in the A/N bond) and its Laplacian V2
rb(BCP) can be used to provide a combined
description of hydrogen bonds and halogen bonds, with correlation coefficients of 0.964 and 0.956,
respectively. The dependence of the interaction strength on the electrostatic potential corresponding to
an electron density of 0.002 a.u. along the R–A bond vector (ESP0.002), the amount of charge transferred
(QCT) and the second-order perturbation stabilization energies of n(NH3) / s*(R–A) (E(2)) were also
examined. Strong halogen-bonded complexes were found to exhibit different linear correlations from
weak halogen-bonded and hydrogen-bonded systems. Nevertheless, for the latter two types of system,
a uniform regression equation can be constructed. These relationships not only improve our
understanding of the nature of halogen bonding but also provide a feasible approach for predicting or
determining the relative strengths of hydrogen bonds and halogen bonds, in particular when both types
of non-covalent interaction coexist and compete with each other.
U2 - 10.1039/c6ra27590g
DO - 10.1039/c6ra27590g
M3 - Article
VL - 7
SP - 10295
EP - 10305
JO - RSC Advances
JF - RSC Advances
SN - 2046-2069
ER -