Lingpeng Meng

Hebei Normal University, Chentow, Hebei, China

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Publications (75)171.82 Total impact

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    ABSTRACT: The positive electrostatic potentials (ESP) outside the σ-hole along the extension of OP bond in OPH3 and the negative ESP outside the nitrogen atom along the extension of the CN bond in NCX could form the Group V σ-hole interaction OPH3 ⋯NCX. In this work, the complexes NCY⋯OPH3 ⋯NCX and OPH3 ⋯NCX⋯NCY (X, YF, Cl, Br) were designed to investigate the enhancing effects of Y⋯O and X⋯N halogen bonds on the P⋯N Group V σ-hole interaction. With the addition of Y⋯O halogen bond, the VS, max values outside the σ-hole region of OPH3 becomes increasingly positive resulting in a stronger and more polarizable P⋯N interaction. With the addition of X⋯N halogen bond, the VS, min values outside the nitrogen atom of NCX becomes increasingly negative, also resulting in a stronger and more polarizable P⋯N interaction. The Y⋯O halogen bonds affect the σ-hole region (decreased density region) outside the phosphorus atom more than the P⋯N internuclear region (increased density region outside the nitrogen atom), while it is contrary for the X⋯N halogen bonds. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.
    Journal of Computational Chemistry 04/2015; DOI:10.1002/jcc.23922 · 3.60 Impact Factor
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    ABSTRACT: The properties of inorganic benzenes have been investigated by means of second-order MøllerPlesset perturbation theory (MP2) calculations and "quantum theory of atoms in molecules" (QTAIM) studies. In this work, the σ and π electron densities were separated from the total electron densities, and therefore it could be possible to evaluate the contributions of σ electrons and π electrons to the chemical bonds and chemical properties of the inorganic benzenes. The following conclusions are given: (1) The π-attractors' positions are correlative with respective atomic radii. With the atom number increasing in the same period, the attractor of π-electron densities becomes closer to respective nucleus. With the atom number increasing in the main group, the position of the π-attractor becomes farther from respective nucleus. (2) For the chemical bonds of the inorganic benzenes rings, their strength is determined by σ-electron densities, not π-electron densities; their bonding character is mainly determined by the σ-electron density, however, the role of π-electron density could not be neglected. (2) For the studied inorganic benzenes, the ELFπ values are relevant with the differences of the electronegativity between the neighboring atoms of the inorganic benzenes rings, Δχ(X,Y). The smaller difference of Δχ(X,Y), the higher value of ELFπ, results in more aromatic properties of the inorganic benzenes.
    The Journal of Physical Chemistry A 02/2015; 119(10). DOI:10.1021/jp511862u · 2.78 Impact Factor
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    ABSTRACT: The influence of metal doping on σ/π-type copper(I)•••thiophene interactions and the nature of Cu•••π/S bonding have been investigated. Our calculated results show that Li, Na, K, Ca and Sc atom doping on thiophene enhance the copper(I)•••thiophene interactions. Enhancement factors are determined by the electrostatic potential of thiophene molecular surface and the electronic configuration of the doping metal. The more negative electrostatic potential, the stronger is the interaction. The influence of the d-block transition metal element (Sc) is larger than that of s-block main group metal elements. Both the σ and π type Cu•••thiophene interaction are of moderate strengths and display partial covalent characters. Linear relationships exist between the topological properties (ρ(rc), ∇2ρ(rc), δ(A, B) and Hc) at the BCP and the bond lengths d(Cu•••π/S). When the Cu•••π/S bond length became shorter, larger ∇2ρ(rc), δ(A, B) and smaller Hc values are to be predicted, resulting in greater covalent character of Cu•••π/S bonding.
    Dalton Transactions 10/2014; 44(3). DOI:10.1039/C4DT02286F · 4.10 Impact Factor
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    ABSTRACT: The electronic structures and bonding characters, the occupation energies of dopants, as well as the formation energies of Frenkel defects in pure LiBH4 center dot NH3 and in Mg- and Al-substituted LiBH4 center dot NH3 were investigated by using first-principles calculations. The occupation energies show that the substitutions with Mg and Al destabilize LiBH4 center dot NH3 and that Mg substitution is easier than Al substitution. Substitution with Mg or Al partly reduced interactions between B-H and N-H atoms, thus improving the dehydrogenation property of LiBH4 center dot NH3. At the same time, substitution with Mg or Al increases the interactions between metal and N atoms, which stabilize the NH3 group and inhibit the release of NH3 during dehydrogenation. The formation energy of Frenkel defects indicates that Mg or Al doping facilitates the formation of Frenkel defects. Our theoretical studies show that Mg and Al are good candidates but Al is better than Mg for improving the dehydrogenation property of LiBH4 center dot NH3. Copyright (c) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
    International Journal of Hydrogen Energy 10/2014; 39(30):17144–17152. DOI:10.1016/j.ijhydene.2014.08.067 · 2.93 Impact Factor
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    ABSTRACT: The nature of metal-metal bonding in [CpM(CO)(3)](2) (M = Cr, Mo, W; Cp = C5H5) was characterized within the framework of the atoms in molecules theory, electron localization function, and molecular formation density difference. Calculated results show that both the electrostatic and the orbital interaction play important roles in the [CpM(CO)(3)](2), and the electrostatic proportions increase in the sequence of M = Cr, Mo, and W. Moreover, the strengths of M-M bond are weaker than single bond. Therefore, the M-M bonds in [CpM(CO)(3)](2) (M = Cr, Mo, and W) cannot be classified as typical covalent single bond. Among them, the Cr-Cr interaction is weak and that Mo-Mo and W-W interactions have moderate strength. They all belong to metallic bonds and have partially covalent characters, the metallic nature of the M-M bond increases in the sequence of Cr, Mo, and W. (c) 2014 Elsevier B.V. All rights reserved.
    Journal of Organometallic Chemistry 10/2014; 769:106–111. DOI:10.1016/j.jorganchem.2014.07.015 · 2.30 Impact Factor
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    ABSTRACT: The nature of E-M bonds in CpE-MCp (E = B, Al, Ga; M = Li, Na, K; Cp = η (5)-C5H5) donor-acceptor sandwiches was studied using the atoms in molecules (AIM) theory, electron localization function (ELF), energy decomposition analysis (EDA), and natural bond orbital analysis (NBO) methods. Both topological and orbital analysis show that the E atom determines the bond strength of the E-M bonds, while the M atom has little influence on it. E-M bond strength decreases in the order E = B, Al, and Ga. The EDA analysis shows that the electrostatic character decreases following the sequence E = B > Al > Ga. Not only the s orbital, but also the p orbital of the E/M atom participates in formation of the E-M bond. The interactions of E and M with Cp are different. The M-Cp interaction is purely electrostatic while the E-Cp interaction has a partly covalent character.
    Journal of Molecular Modeling 10/2014; 20(10):2455. DOI:10.1007/s00894-014-2455-6 · 1.87 Impact Factor
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    ABSTRACT: Halogen bonding (XB) as an emerging noncovalent interaction, due to its highly directional and devisable, has given rise to considerable interest for constructing supramolecular assemblies. In this work, the newly developed density functional M06-2X calculations and the quantum theory of "atoms in molecules" (QTAIM) studies were carried out on a series of N•••I halogen bonding to investigate the influence of Lewis bases (XB acceptors) on the XB. For the Lewis base C6-nH6-nNn (n = 1, 2, 3), with the increasing number of nitrogen atom in the aromatic ring, the most negative electrostatic potentials (VS, min) outside the nitrogen atom becomes less negative and the XB becomes weaker. The positive cooperativity exists in the Y--C6H5N•••C6F5I, Y--C4H4N2•••C6F5I, and Y--C3H3N3•••C6F5I (Y- = Cl-, Br-, I-) termolecular complexes: the H-bond or anion-π interactions have the ability to enhance the N•••I halogen bond, and vice versa. With the addition of halogen anions to the XB acceptor, the XB become more covalent, more electronic charge transfer from the XB acceptors to donors, the XB acceptors become more energetic stabilization and XB donors become more destabilization, the atomic volume attraction of both the nitrogen and iodine atoms become more obvious. From the view of the Laplacian of electron density function, for the XB acceptor, the reactivity zone is the region of valence shell charge concentration (VSCC), where have a (3, -3) critical point (CP) and referred to as lump, thus the XB interaction can be classified as lump-hole interaction. The more negative of VS,min outside the nitrogen atom, the stronger of the XB, resulting in the greater of the distance between the (3, -3) CP and the nitrogen nucleus.
    The Journal of Physical Chemistry A 08/2014; 118(34). DOI:10.1021/jp502558p · 2.78 Impact Factor
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    ABSTRACT: The σ-hole interaction, which occurs between the covalent IV-VII atoms and nucleophilic substances, has become a hot issue of weak interaction. In this work, NCFO[double bond, length as m-dash]PX3(NCF)n (X = F, Cl, Br, H, CH3; n = 0, 1, 2) complexes were constructed and studied based on the second-order Møller-Plesset perturbation theory (MP2) calculations to investigate the enhancing effects of group V σ-hole interactions on the FO halogen bond. With increasing n, the FO halogen bond becomes stronger, indicating that the group V σ-hole interactions could enhance the FO halogen bond. As the capacity of donating electrons of X increases, the most negative electrostatic potentials outside the oxygen atom of O[double bond, length as m-dash]PX3(NCF)n (n = 0, 1, 2) become more negative, resulting in a stronger FO halogen bond. In the formation of a FO halogen bond, along the sequence of X = F, Cl, Br, H, CH3 of the negative sites O[double bond, length as m-dash]PX3, the electric field of the lone pair of oxygen becomes greater and causes a larger decrease in electron density outside the fluorine atom. On the other hand, with increasing n from 0 to 2, the group V σ-hole interactions also increase the electric field of lone pair of oxygen and results in a larger decrease in electron density outside the fluorine atom.
    Physical Chemistry Chemical Physics 08/2014; 16(36). DOI:10.1039/c4cp02430c · 4.20 Impact Factor
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    ABSTRACT: Factors affecting the Cu•••Cu distance in copper(I) complexes with the N-heterocyclic carbene (NHC), Bis-NHC and N-phosphinomethyl-functionalized NHC (NHCP) ligands have been investigated by quantum chemistry and topological analysis of electron density. The calculated results show that the ligands, ring size and shape, substitution pattern of NHC/NHCP, and overall charge of the system are factors that affect the Cu•••Cu distance. The NHC ligand and an overall positive charge of the system lead to short Cu•••Cu distance. Topological analysis shows that there are attractions between the two Cu atoms. And the Cu•••Cu attractions in the eight-membered systems and in the 10-membered cation systems are moderately strong and belong to closed-shell type, which have partially covalent shared-closed interactions. Whereas the same interactions in the 12-membered cation system and in the neutral system with Br are weak and belong to closed-closed interactions.
    New Journal of Chemistry 07/2014; 38(12). DOI:10.1039/C4NJ00918E · 3.16 Impact Factor
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    ABSTRACT: The influences of Cr and Zr dopants on the electronic structure and the hydrogen adsorption of the Mg2Ni (0 1 0) surface have been studied by using the first-principles method. The calculated results show that Cr/Zr substitutions increase the activity of the Mg2Ni (0 1 0) surface, reduce the Ni–Mg and Ni–Ni interactions in Mg2Ni, and increase the hollow size between two atoms, which would aid hydrogen adsorption and further diffusion. As the hydrogen absorbs on clean Mg2Ni (0 1 0) surface, three stable hydrogen absorption sites are determined: the top sites of the Ni atom as well as the Ni–Ni and Mg–Ni bridge sites. Substituting the Ni atoms on the Mg2Ni (0 1 0) surface with Cr or Zr increase the number of stable hydrogen adsorption sites, decrease the hydrogen adsorption energy, and improve the hydrogen storage capacity of Mg2Ni. For both clean and Cr/Zr-doped Mg2Ni (0 1 0) surfaces, the most stable adsorption site is the Ni–M (M = Ni, Cr, or Zr) bridge site. Density of states calculations show that the adsorption on Ni–M bridge site occurs from the overlap of the H 1s and M outermost s states. All of the calculated results show Zr and Cr atoms, especial Zr atom, to be good candidates for improving the hydrogen storage capacity of Mg2Ni.
    Journal of Alloys and Compounds 07/2014; 601:280–288. DOI:10.1016/j.jallcom.2014.02.176 · 2.73 Impact Factor
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    ABSTRACT: Cooperativity between the H/Cl···C bonds of XH/XCl···CH2PH3 and the P···N interaction of CH2PH3···NH3 in XH/XCl···CH2PH3···NH3 (X = F, N3, CN, CCCN, CCF) was investigated by performing second-order Møller-Plesset perturbation theory (MP2) calculations and quantum theory of atoms in molecules (QTAIM) studies. The formation of a hydrogen/halogen bond greatly extends the scope and increases the most positive electrostatic potential of the σ-hole on the outer surface of the phosphorus atom. This increases the P···N interaction energy, the electron density at the P···N bond critical point, the electrostatic character of the P···N interaction, and it decreases the P···N interaction distance. The net result is that the formation of a hydrogen/halogen bond enhances the P···N interaction, and vice versa. However, the P···N interaction is enhanced by the presence of the hydrogen or halogen bond to a much greater degree than the hydrogen or halogen bond is enhanced by the P···N interaction.
    Journal of Molecular Modeling 06/2014; 20(6):2282. DOI:10.1007/s00894-014-2282-9 · 1.87 Impact Factor
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    ABSTRACT: The structures and dehydrogenation properties of pure and Ti/Ni-doped Mg(AlH4)(2) were investigated using the first-principles calculations. The dopants mainly affect the geometric and electronic structures of their vicinal AlH4 units. Ti and Ni dopants improve the dehydrogenation of Mg(AlH4)(2) in different mechanisms. In the Ti-doped case, Ti prefers to occupy the 13-hedral interstice (Ti-iA) and substitute for the Al atom (Ti-Al), to form a highcoordination structure TiHn (n = 6, 7). The Ti 3d electrons hybridize markedly with the H 1s electrons in Ti-Al and with the Al 3p electrons in Ti, which weakens the Al H bond of adjacent AlH4 units and facilitates the hydrogen dissociation. A TiAl3H13 intermediate in Ti-iA is inferred as the precursor of Mg(AlH4)(2) dehydrogenation. In contrast, Ni tends to occupy the octahedral interstice to form the NiH4 tetrahedron. The tight bind of the Ni with its surrounding H atoms inhibits their dissociation though the nearby Al H bond also becomes weak. Therefore, Ti is the better dopant candidate than Ni for improving the dehydrogenation properties of Mg(AlH4)(2) because of its abundant activated hydrogen atoms and low hydrogen removal energy. Copyright
    International Journal of Hydrogen Energy 06/2014; 39(17). DOI:10.1016/j.ijhydene.2014.04.051 · 2.93 Impact Factor
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    ABSTRACT: The nature of the interactions of cyanide with lithium and hydrogen halides was investigated using ab initio calculations and topological analysis of electron density. The computed properties of the lithium-bonded complexes RCN···LiX (R = H, F, Cl, Br, CCH, CHCH2, CH3, C2H5; X = Cl, Br) were compared with those of corresponding hydrogen-bonded complexes RCN···HX. The results show that both types of intermolecular interactions are “closed-shell” noncovalent interactions. The effect of substitution on the interaction energy and electron density at the bond critical points of the lithium and hydrogen bonding interactions is similar. In comparison, the interaction energies of lithium-bonded complexes are more negative than those of hydrogen-bonded counterparts. The electrostatic interaction plays a more important role in the lithium bond than in the hydrogen bond. On complex formation, the net charge and energy of the Li atom decrease and the atomic volume increases, while the net charge and energy of the H atom increase and the atomic volume decreases. © 2013 Wiley Periodicals, Inc.
    International Journal of Quantum Chemistry 03/2014; 114(6). DOI:10.1002/qua.24577 · 1.17 Impact Factor
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    ABSTRACT: The second-order Moller-lesset perturbation theory (MP2) calculations have been performed to investigate the cooperativity between the sigma-hole and pi-hole interactions in the ClO center dot center dot center dot XONO2/XONO center dot center dot center dot NH3 (X = Cl, Br, I) complexes. The sigma-holes and pi-holes have been found on the outer surfaces of XONO2/XONO: the sigma-hole is outside the halogen atoms approximately along the extension of X-O bond, and the pi-hole is above and below the nitrogen atom and the terminal oxygen atom. Both the sigma-hole and pi-hole interaction energies are consistent with the most positive electrostatic potentials (V-S,V- max) of the sigma-holes and pi-holes, indicating that electrostatic interactions play an important role in the sigma-hole and pi-hole interactions. From a two-to a three-body interaction, the interaction energies, binding distances, and infrared vibrational frequencies prove that there is negative cooperativity between the sigma-hole and pi-hole interactions. In the formation of the sigma-hole and pi-hole interactions, the electric fields of the negative sites ClO and NH3 cause the decrease of the electronic density of the sigma-hole and pi-hole regions of XONO2. Due to the negative effect between the sigma-hole and pi-hole interactions, the decreased regions of electronic density of the sigma-hole and pi-hole are somewhat contracted.
    Structural Chemistry 02/2014; 26(1):213-221. DOI:10.1007/s11224-014-0486-3 · 1.90 Impact Factor
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    ABSTRACT: Halogen bonding interactions are highly directional intermolecular interactions that are often important in crystal engineering. In this work, second-order MøllerPlesset perturbation theory (MP2) calculations, and quantum theory of "atoms in molecules" (QTAIM) and non-covalent interaction (NCI) studies were carried out on a series of X•••N halogen bonds between substituted haloperfluoroarenes C6F4XY (X = Cl, Br, I; Y = F, CN, NO2) as bond donors and 1,2-diaminoethane as bond acceptor. Our research supports earlier work that electron-withdrawing substituents produce an enhancement effect on the size of the σ-hole and the maximum positive electrostatic potentials (VS,max), which further strengthens the halogen bonding. The metallic ion M+ (M+ = Li+, Na+) has the ability to enhance the size of both the σ-hole and VS,max value with the formation of [MNCC6F4X]+, resulting in more electronic charge transfer away from the halogen atom X and an increase in the strength of the halogen bond. It is found that the values of VS,max at the σ-holes are linear in relation to the halogen-bonded interaction energies and the halogen bonding interaction distance, indicating that the electrostatic interaction plays a key role in the halogen bonding interactions. The values of VS,max at the σ-holes are also linear in relation to the electron density, its Laplacian and -Gb/Vb of XB, indicating that the topological properties and energy properties at the BCPs are correlated with the electrostatic potentials.
    The Journal of Physical Chemistry A 11/2013; 117(48). DOI:10.1021/jp408151t · 2.78 Impact Factor
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    ABSTRACT: We presented a theoretical study on the detailed reaction mechanism and kinetics of the CN radical with the HNCS molecule. The barrierless minimum energy path and the most favorable entrance channel have been determined by constructing a two-dimensional potential energy surface of the C atom of CN attacking the HNCS molecule. The reaction of the C atom attacking the S atom was finally identified as the dominant entrance channel based on the rate constants' results calculated with the canonical variational transition state theory. The master equation method was employed to calculate the products' branching ratios, the overall rate constant, and the pressure dependence of the title reaction. The B3LYP∕6-311+G(2d,p) method was employed for all the geometrical optimizations and a multi-level extrapolation method based on the CCSD(T) and MP2(FC) energies was employed for further energy refinements.
    The Journal of Chemical Physics 10/2013; 139(15):154307. DOI:10.1063/1.4825080 · 3.12 Impact Factor
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    ABSTRACT: The positive electrostatic potentials (σ-hole) have been found in ylides CH2XH3 (X = P, As, Sb) and CH2YH2 (Y = S, Se, Te), on the outer surfaces of group VA and VIA atoms, approximately along the extensions of the C-X and C-Y bonds, respectively. These electrostatic potentials suggest that the above ylides can interact with nucleophiles to form weak, directional noncovalent interactions similar to halogen bonding interactions. MP2 calculations have confirmed the formation of CH2XH3···HM complexes (X = P, As, Sb; M = BeH, ZnH, MgH, Li, Na). The interaction energies, interaction distances, topological properties (electron density and its Laplacian), and energy properties (kinetic electron energy density and potential electron energy density) at the X(1)···H(10) bond critical points are all correlated with the most negative electrostatic potential value of HM, indicating that electrostatic interactions play an important role in these weak X···H interactions. Similar to the halogen bonding interactions, weak interactions involving ylides may be significant in several areas such as organic synthesis, crystal engineering, and design of new materials.
    Journal of Molecular Modeling 09/2013; 19(11). DOI:10.1007/s00894-013-1992-8 · 1.87 Impact Factor
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    ABSTRACT: The nature of the E–E bonds in heavier ditetrel alkyne analogues ArEEAr (Ar = C6H3-2,6(C6H3-2,6-Pri2)2; E = Si, Ge, Sn, Pb) have been studied by topological analysis of the electron localization function (ELF), the delocalization index from the atoms in molecules (AIM) theory and bond orbital analysis. Both the topological and the orbital analysis show that the nature of the E–E bonds in ArEEAr are different to that of the classical covalent triple CC bond of ArCCAr. In ArEEAr, all of the E–E bonds display charge-shift character; the ELF valence basin centroids of the E–E (E = Ge, Sn) bond do not occupy the central region between the two atoms, but have, in effect, fled that region and split into two kinds of basins. In addition, more and more electrons are transferred from the bond basins of the E–E bond to the lone pair basin of the E atoms, which means that a great portion of the bonding components comes from the lp (lone-pair) orbitals of the E atom rather than the electron-sharing bond, as in acetylene. Furthermore, the strength of the E–E bond decreases in the sequence of E = Si, Ge, Sn, and Pb.
    New Journal of Chemistry 09/2013; 37(10). DOI:10.1039/C3NJ00600J · 3.16 Impact Factor
  • International Journal of Hydrogen Energy 08/2013; 38(26):11303-11312. DOI:10.1016/j.ijhydene.2013.06.099 · 2.93 Impact Factor
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    ABSTRACT: The influences of the Li⋅⋅⋅π interaction of C6 H6 ⋅⋅⋅LiOH on the H⋅⋅⋅π interaction of C6 H6 ⋅⋅⋅HOX (X=F, Cl, Br, I) and the X⋅⋅⋅π interaction of C6 H6 ⋅⋅⋅XOH (X=Cl, Br, I) are investigated by means of full electronic second-order Møller-Plesset perturbation theory calculations and "quantum theory of atoms in molecules" (QTAIM) studies. The binding energies, binding distances, infrared vibrational frequencies, and electron densities at the bond critical points (BCPs) of the hydrogen bonds and halogen bonds prove that the addition of the Li⋅⋅⋅π interaction to benzene weakens the H⋅⋅⋅π and X⋅⋅⋅π interactions. The influences of the Li⋅⋅⋅π interaction on H⋅⋅⋅π interactions are greater than those on X⋅⋅⋅π interactions; the influences of the H⋅⋅⋅π interactions on the Li⋅⋅⋅π interaction are greater than X⋅⋅⋅π interactions on Li⋅⋅⋅π interaction. The greater the influence of Li⋅⋅⋅π interaction on H/X⋅⋅⋅π interactions, the greater the influences of H/X⋅⋅⋅π interactions on Li⋅⋅⋅π interaction. QTAIM studies show that the intermolecular interactions of C6 H6 ⋅⋅⋅HOX and C6 H6 ⋅⋅⋅XOH are mainly of the π type. The electron densities at the BCPs of hydrogen bonds and halogen bonds decrease on going from bimolecular complexes to termolecular complexes, and the π-electron densities at the BCPs show the same pattern. Natural bond orbital analyses show that the Li⋅⋅⋅π interaction reduces electron transfer from C6 H6 to HOX and XOH.
    ChemPhysChem 06/2013; 14(8). DOI:10.1002/cphc.201300075 · 3.36 Impact Factor