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Fluorines in tetrafluoromethane as halogen bond donors: Revisiting address the nature of the fluorine's σ hole
Author(s) -
Varadwaj Arpita,
Varadwaj Pradeep R.,
Jin BihYaw
Publication year - 2015
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24877
Subject(s) - chemistry , fluorine , basis set , halogen , lewis acids and bases , non covalent interactions , atoms in molecules , natural bond orbital , density functional theory , computational chemistry , halogen bond , hydrogen bond , molecule , covalent bond , hydrogen fluoride , atomic physics , chemical physics , physics , inorganic chemistry , organic chemistry , alkyl , catalysis
It has been demonstrated in several instances that the 0.001 a.u. (electrons per bohr 3 ) isodensity mapped electrostatic surface potentials on the fluorines along the outermost extensions of the CF covalent bonds in tetrafluoromethane (CF 4 ) are entirely negative, they are thereby unable to engage in σ hole bonding interactions with the negative sites on another molecules. In this study, we have attempted at resolving this controversy by performing various high‐level electronic structure calculations with Quadratic Configuration Integrals of Singles and Doubles QCISD(full), second‐order Møller–Plesset MP2(full), and 12 other Density Functional Theory (DFT) based functionals with and without dispersion corrections, all in conjunction with the 6–311++G(2d,2p) basis set. The results achieved with all the levels of theory utilized suggest that the fluorine's σ holes in CF 4 are positive regardless of the 0.001‐, 0.0015‐, and 0.002‐a.u. isodensity mapped electrostatic surfaces examined. Because of this specific quality, the fluorines in CF 4 have displayed their capacities to form not only 1:1 clusters with the Lewis bases such as water (H 2 O), ammonia (NH 3 ), formaldehyde (H 2 CO), hydrogen fluoride (HF), and hydrogen cyanide (HCN), but also 1:2, 1:3, and 1:4 clusters with the latter three randomly chosen Lewis bases. Various topological and nontopological features obtained from applications of atoms in molecules, noncovalent interaction reduced‐density‐gradient and natural bond orbital analytical tools reveal that the N···F, O···F, and F···F long‐ranged interactions developed between the interacting monomers in H 3 N···FCF 3 , H 2 O···FCF 3 , and (YD) n =1–4 ···F 4 C (YD = H 2 CO, HCN, and HF) are reminiscent of halogen bonding. The nonadditive cooperative and anticooperative energetic effects emerged on cluster formations are discussed in detail. © 2015 Wiley Periodicals, Inc.