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Electrostatics and ...
Electrostatics and polarization determine the strength of the halogen bond : a red card for charge transfer
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- Brinck, Tore, 1965- (author)
- KTH,Tillämpad fysikalisk kemi
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- Nyberg Borrfors, Andre (author)
- KTH,Tillämpad fysikalisk kemi,CBH, Dept Chem, Appl Phys Chem, SE-10044 Stockholm, Sweden.
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(creator_code:org_t)
- 2019-04-24
- 2019
- English.
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In: Journal of Molecular Modeling. - : Springer Nature. - 1610-2940 .- 0948-5023. ; 25:5
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https://doi.org/10.1...
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Abstract
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- A series of 20 halogen bonded complexes of the types R-Br center dot center dot center dot Br- (R is a substituted methyl group) and R '-CC-Br center dot center dot center dot Br- are investigated at the M06-2X/6-311+G(d,p) level of theory. Computations using a point-charge (PC) model, in which Br- is represented by a point charge in the electronic Hamiltonian, show that the halogen bond energy within this set of complexes is completely described by the interaction energy (E-PC) of the point charge. This is demonstrated by an excellent linear correlation between the quantum chemical interaction energy and E-PC with a slope of 0.88, a zero intercept, and a correlation coefficient of R-2=0.9995. Rigorous separation of E-PC into electrostatics and polarization shows the high importance of polarization for the strength of the halogen bond. Within the data set, the electrostatic interaction energy varies between 4 and-18kcal mol(-1), whereas the polarization energy varies between -4 and-10kcal mol(-1). The electrostatic interaction energy is correlated to the sum of the electron-withdrawing capacities of the substituents. The polarization energy generally decreases with increasing polarizability of the substituents, and polarization is mediated by the covalent bonds. The lower (more favorable) E-PC of CBr4---Br- compared to CF3Br center dot center dot center dot Br- is found to be determined by polarization as the electrostatic contribution is more favorable for CF3Br center dot center dot center dot Br-. The results of this study demonstrate that the halogen bond can be described accurately by electrostatics and polarization without any need to consider charge transfer.
Subject headings
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
Keyword
- Halogen bonding
- Electrostatic potential
- Induction
- Charge transfer
- Energy decomposition
- Sigma-hole
Publication and Content Type
- ref (subject category)
- art (subject category)
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