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Revealing the physical nature and the strength of charge‐inverted hydrogen bonds by SAPT(DFT), MP2, SCS‐MP2, MP2C, and CCSD(T) methods
Author(s) -
Yourdkhani Sirous,
Jabłoński Mirosław
Publication year - 2017
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24739
Subject(s) - basis set , hydrogen bond , chemistry , extrapolation , dimer , charge (physics) , intramolecular force , binding energy , computational chemistry , atomic physics , molecule , physics , quantum mechanics , stereochemistry , density functional theory , mathematical analysis , mathematics , organic chemistry
The physical nature of charge‐inverted hydrogen bonds in H 3 XH ⋯ YH 3 (X = Si, Ge; Y = Al, Ga) dimer systems is studied by means of the SAPT(DFT)‐based decomposition of interaction energies and supermolecular interaction energies based on MP2, SCS‐MP2, MP2C, and CCSD(T) methods utilizing dimer‐centered aug‐cc‐pCVnZ (n = D, T, Q) basis sets as well as an extrapolation to the complete basis set limit. It is revealed that charge‐inverted hydrogen bonds are inductive in nature, although dispersion is also important. Computed interaction energies form the following relation:E int SAPT< E int SCS − MP 2≤ E int MP 2 C< E int MP 2≈ E int CCSD ( T ). It is confirmed that the aug‐cc‐pCVDZ basis set performs poorly and that very accurate values of interaction and dispersion energies require basis sets of at least quadrupole‐ ζ quality. Considerably large binding energies suggest potential usefulness of charge‐inverted hydrogen bonds as an important structural motif in molecular binding. Terminology applying to σ ‐ and π ‐hole interactions as well as to triel and tetrel bonds is discussed. According to this new terminology the charge‐inverted hydrogen bond would become the first described case of a hydride‐triel bond. © 2017 Wiley Periodicals, Inc.