Lingpeng Meng

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Organization: Hebei Normal University

Department: College of Chemistry and Material Science

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References

Mechanism and kinetics for the reactions of methacrolein and methyl vinyl ketone with HO2 radical

Co-reporter:Cuihong Sun;Yanli Zeng;Baoen Xu

New Journal of Chemistry (1998-Present) 2017 vol. 41(Issue 15) pp:7714-7722

Publication Date(Web):2017/07/24

DOI:10.1039/C7NJ01260H

The high-level theoretical study on the reactions of methacrolein and methyl vinyl ketone with hydroperoxyl radical was carried out using the M06-2X method in conjunction with the 6-311+G(2df,2pd) basis sets. For the two reactions, all possible addition and abstraction channels initiate from the reactant complexes. The most favorable reaction channel is the concerted addition of the terminal O atom of HO2 radical to the aldehyde-C (or carbonyl-C) and H-transfer from HO2 to the aldehyde-O (or carbonyl-O) forming the α-hydroxyalkenylperoxy radical. For the methacrolein + HO2 and methyl vinyl ketone + HO2 reactions, the calculated rate constants decrease as the temperature increases from 200 K to 500 K, and at 298 K, they are 1.34 × 10−14 and 2.56 × 10−14 cm3 molecule−1 s−1, respectively. The calculated results are close to the previous theoretical and experimental observations for the reactions of HO2 radical with formaldehyde, acetaldehyde, and acetone.

Dinuclear first-row transition metal–(C8Me6)2 complexes: metal–metal and metal–ligand bonds determined by the d electron configuration of the metal atom

Co-reporter:Xiuli Yan, Xiaoyan Li, Zheng Sun, Qingzhong Li and Lingpeng Meng

New Journal of Chemistry 2016 vol. 40(Issue 3) pp:1988-1996

Publication Date(Web):10 Nov 2015

DOI:10.1039/C5NJ02469B

The metal–metal and metal–ligand bonds in the bimetallic sandwich compounds Pn*2M2 (Pn* = C8Me6; M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) have been investigated using the atoms in molecules (AIM) theory, electron location function (ELF), and electron decomposition analysis (EDA). The calculated results indicate that the strength of the metal–metal (M–M) bond and the coordination mode of the Pn* ligands to a pair of metal atoms depend on the d electron configuration of the transition metal. The more unpaired d electrons, the higher the coordination number of the metal to the ligands, which increases from η1 to η5. The stronger the metal–ligand interaction, the weaker the contribution of the electrostatic interaction to the metal–ligand interaction. The strength of the M–M bonds increases in the sequence M = Sc < Ti < V, and decreases in the sequence V > Cr > Mn > Fe > Co > Ni > Cu. The V–V bond is the strongest of the studied dinuclear first-row transition metal–(C8Me6)2 complexes. The studied M–M bonds are metallic bonds and have a partially covalent character, except for Sc–Sc which is a covalent bond and Cu–Cu which is an electrostatic interaction.

Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde

Co-reporter:Lixin Mo;Yanli Zeng;Xiaoyan Li;Xueying Zhang

Journal of Molecular Modeling 2016 Volume 22( Issue 7) pp:

Publication Date(Web):2016 July

DOI:10.1007/s00894-016-3037-6

The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)−S bonds, and two σ-holes upon extension of S−Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F−S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX′2 (X = F, Cl, Br, and X′ = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds.

Influences of the substituents on the M–M bonding in Cp4Al4 and Cp2M2X2 (M = B, Al, Ga; Cp = C5H5, X = halogen)

Co-reporter:Feifei Lu, Xiaoyan Li, Zheng Sun, Yanli Zeng and Lingpeng Meng

Dalton Transactions 2015 vol. 44(Issue 31) pp:14092-14100

Publication Date(Web):30 Jun 2015

DOI:10.1039/C5DT01901J

Although the geometries of Cp*4Al4 (Cp* = C5Me5) and Cp4Al4 (Cp = C5H5) are similar, Cp*4Al4 is more stable than Cp4Al4. Cp*2Al2I2 is the first complex involving an Al(II)–Al(II) bond to be supported by Cp-type ligands. In this work, the stability of Cp*4Al4 and Cp4Al4 (Cp = C5H5), the nature of M–M bonding in Cp2M2X2 (M = B, Al, and Ga), and the influences of the X atom on the M–M bonds have been analyzed and compared within the framework of the atoms in molecules (AIM) theory, electron localization function (ELF), energy decomposition analysis (EDA), and natural bond orbital (NBO) analysis. The calculated results show that Cp*4Al4 is more stable than Cp4Al4 because of H⋯H interactions between the methyl groups on the same and different Cp rings and not because of the Al–Al bonds. In Cp2M2X2, the B–B bond is stronger than the Al–Al and Ga–Ga bonds. The B–B bond is most consistent with covalent bonding, whereas the Al–Al and Ga–Ga bonds are more consistent with metallic bonding. The strengths of the B–B bond increase in the sequence X = F, Cl, Br, and I, whereas the Al–Al and Ga–Ga bonds decrease in the sequence X = F, Cl, Br, and I. The different change tendencies arise from the different M–M bonds and the orbital interactions between atoms X and M.

Enhancing σ/π-type copper(I)⋯thiophene interactions by metal doping (metal = Li, Na, K, Ca, Sc)

Co-reporter:Xiayan Zhang, Xiaoyan Li, Yanli Zeng, Shijun Zheng and Lingpeng Meng

Dalton Transactions 2015 vol. 44(Issue 3) pp:1283-1291

Publication Date(Web):15 Oct 2014

DOI:10.1039/C4DT02286F

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 enhances the copper(I)⋯thiophene interactions. Enhancement factors are determined by the electrostatic potential of the thiophene molecular surface and the electronic configuration of the doping metal. The more negative the 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 interactions 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 can be predicted, resulting in greater covalent character of Cu⋯π/S bonding.

Influences of Al, Ti and Nb doping on the structure and hydrogen storage property of Mg(BH4)2(001) surface – A theoretical study

Co-reporter:Nannan Sun, Baoen Xu, Shasha Zhao, Zheng Sun, Xiaoyan Li, Lingpeng Meng

International Journal of Hydrogen Energy 2015 Volume 40(Issue 33) pp:10516-10526

Publication Date(Web):7 September 2015

DOI:10.1016/j.ijhydene.2015.06.128

•In Mg(BH4)2(001) surface, substitution of Mg with Ti is easier than with Al and Nb.•Ti and Nb substitutions facilitate H dissociation in Mg(BH4)2(001) surface.•Ti and Nb substitutions reduce the energy barrier and do favour H diffusion.First-principles calculations were performed to investigate the influences of Al, Ti and Nb doping on the structure, the hydrogen dissociation energy, the electronic structure and the diffusion path of H atom in Mg(BH4)2(001) surface. The calculated occupation energies indicate that substitution of Mg atom with Ti is the easiest, with Al is a little harder, and with Nb is the most difficult. The doping can reduce the strengths of B–H bonds around the dopants thus favours the dissociation of these H atoms. In comparison, the Nb doping shows the most outstanding effect and the Al doping has the least influence on the dissociation of hydrogen atoms. The minimum energy pathways (MEP) calculations indicate that the substitutions with Ti and Nb can reduce the energy barriers of hydrogen diffusion and thus facilitate H diffusion in the Mg(BH4)2(001) surface, whereas the substitution with Al is not an effective technique for improving the hydrogenation/dehydrogenation performance of Mg(BH4)2.The substitutions of Ti and Nb for Mg can favour the hydrogen dissociation and facilitate the hydrogen diffusion in Mg(BH4)2(001) surface, whereas Al substitution is not an effective technique.

Influence of titanium and nickel dopants on the dehydrogenation properties of Mg(AlH4)2: Electronic structure mechanisms

Co-reporter:Baoen Xu, Cuihong Sun, Xiaoyan Li, Yanli Zeng, Xueying Zhang, Lingpeng Meng

International Journal of Hydrogen Energy 2014 Volume 39(Issue 17) pp:9276-9287

Publication Date(Web):5 June 2014

DOI:10.1016/j.ijhydene.2014.04.051

•The Ti/Ni doping prefers to occupy the interstice in bulk Mg(AlH4)2.•TiAl3H13 intermediate is inferred as the precursor of Mg(AlH4)2 dehydrogenation.•The bonding of Ti/Ni–Al and Ti/Ni–H can facilitate the Al–H bond dissociation.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 (TiiA) and substitute for the Al atom (TiAl), to form a high-coordination structure TiHn (n = 6, 7). The Ti 3d electrons hybridize markedly with the H 1s electrons in TiAl and with the Al 3p electrons in TiiA, which weakens the Al–H bond of adjacent AlH4 units and facilitates the hydrogen dissociation. A TiAl3H13 intermediate in TiiA 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.The influences of Ti and Ni dopants on the dehydrogenation properties of Mg(AlH4)2 are investigated using the first-principles calculations. Ti and Ni dopants improve the dehydrogenation of Mg(AlH4)2 in different mechanisms.

Influence of Cr/Zr doping on the electronic structure and hydrogen storage properties of the Mg2Ni (0 1 0) surface: A first principles study

Co-reporter:Baoen Xu, Mingyue Li, Xiaoyan Li, Peisi Zhang, Lingpeng Meng

Journal of Alloys and Compounds 2014 Volume 601() pp:280-288

Publication Date(Web):15 July 2014

DOI:10.1016/j.jallcom.2014.02.176

•Cr/Zr substitution increases the activity of the Mg2Ni (0 1 0) surface.•Cr/Zr atoms, especially Zr, are good candidates for improving hydrogen storage capacity of Mg2Ni.•Ni–M (M = Ni, Zr, Cr) bridge site is the most stable hydrogen adsorption site.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.

Regulatory factors and the nature of Cu⋯Cu interaction in copper(I) complexes with NHC and NHCP ligands: a theoretical assessment

Co-reporter:Feifei Lu, Xiaoyan Li, Yanli Zeng, Xueying Zhang and Lingpeng Meng

New Journal of Chemistry 2014 vol. 38(Issue 12) pp:5786-5792

Publication Date(Web):30 Jul 2014

DOI:10.1039/C4NJ00918E

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 and 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 a 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 the 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.

Effects of Mg and Al doping on the electronic structure and dehydrogenation of LiBH4·NH3

Co-reporter:Peisi Zhang, Baoen Xu, Xiaoyan Li, Yanli Zeng, Lingpeng Meng

International Journal of Hydrogen Energy 2014 Volume 39(Issue 30) pp:17144-17152

Publication Date(Web):13 October 2014

DOI:10.1016/j.ijhydene.2014.08.067

•Mg/Al substitution improves the dehydrogenation property of LiBH4·NH3.•Mg or Al doping facilitates the formation of Frenkel defects.•Al is better than Mg for improving the dehydrogenation property of LiBH4·NH3.The electronic structures and bonding characters, the occupation energies of dopants, as well as the formation energies of Frenkel defects in pure LiBH4·NH3 and in Mg- and Al-substituted LiBH4·NH3 were investigated by using first-principles calculations. The occupation energies show that the substitutions with Mg and Al destabilize LiBH4·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·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·NH3.The influences of Mg and Al dopants on the dehydrogenation properties of LiBH4·NH3 are investigated using the first-principles calculations. Mg and Al are good candidates but Al is better than Mg for improving the dehydrogenation property of LiBH4·NH3.

N···I Halogen Bonding Interactions: Influence of Lewis Bases on Their Strength and Characters

Co-reporter:Na Han, Yanli Zeng, Cuihong Sun, Xiaoyan Li, Zheng Sun, and Lingpeng Meng

The Journal of Physical Chemistry A 2014 Volume 118(Issue 34) pp:7058-7065

Publication Date(Web):August 7, 2014

DOI:10.1021/jp502558p

Halogen bonding (XB) as an emerging noncovalent interaction, due to its highly directional and devisable properties, 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 energetically stabilized and XB donors become more destabilized, and 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 it is a (3, −3) critical point (CP) and referred to as a lump, thus the XB interaction can be classified as a lump–hole interaction. The more negative VS,min outside the nitrogen atom, the stronger the XB, resulting in the greater distance between the (3, −3) CP and the nitrogen nucleus.

First-principles study of hydrogen vacancies in lithium amide doped with titanium and niobium

Co-reporter:Liping Cheng, Baoen Xu, Xuejing Gong, Xiaoyan Li, Yanli Zeng, Lingpeng Meng

International Journal of Hydrogen Energy 2013 Volume 38(Issue 26) pp:11303-11312

Publication Date(Web):30 August 2013

DOI:10.1016/j.ijhydene.2013.06.099

Influence of the Li Interaction on the H/X Interactions in HOLiC6H6HOX/XOH (X=F, Cl, Br, I) Complexes

Co-reporter: Yanli Zeng;Dr. Wenjie Wu;Dr. Xiaoyan Li; Shijun Zheng ; Lingpeng Meng

ChemPhysChem 2013 Volume 14( Issue 8) pp:1591-1600

Publication Date(Web):

DOI:10.1002/cphc.201300075

Abstract

The influences of the Li⋅⋅⋅π interaction of C₆H₆⋅⋅⋅LiOH on the H⋅⋅⋅π interaction of C₆H₆⋅⋅⋅HOX (X=F, Cl, Br, I) and the X⋅⋅⋅π interaction of C₆H₆⋅⋅⋅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 C₆H₆⋅⋅⋅HOX and C₆H₆⋅⋅⋅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 C₆H₆ to HOX and XOH.

Metal–Metal and Metal–Ligand Bonds in (η5-C5H5)2M2 (M = Be, Mg, Ca, Ni, Cu, Zn)

Co-reporter:Xiaoyan Li, Suhong Huo, Yanli Zeng, Zheng Sun, Shijun Zheng, and Lingpeng Meng

Organometallics 2013 Volume 32(Issue 4) pp:1060-1066

Publication Date(Web):February 1, 2013

DOI:10.1021/om301110j

The metal–metal and metal–ligand bonds in a series of binuclear metallocenes (η5-C5H5)2M2 (M = Be, Mg, Ca, Ni, Cu, Zn) have been characterized within the framework of the atoms in molecules (AIM) theory, electron localization function (ELF), and molecular formation density difference (MFDD). The calculated results show that the metal–metal bonds in the binuclear main-group-metal metallocenes are different from those in binuclear transition-metal metallocenes. In binuclear main-group-metal metallocenes, the metal–metal bonds are linked by two metal–“non-nuclear attractor (NNA)” bonds, while such NNAs do not exist in the binuclear transition-metal metallocenes. In addition, the transition-metal–transition-metal bonds are more delocalized than those of the main-group-metal–main-group-metal bonds. The main-group-metal–main-group-metal bonds show covalent characteristics while the transition-metal–transition-metal bonds display “closed shell” ionic characteristics. The metal–ligand bonds are mainly ionic. There are both σ and π characteristics in the metal–ligand interactions, and the π interaction is predominant.

Enhancing Effects of Electron-Withdrawing Groups and Metallic Ions on Halogen Bonding in the YC6F4X···C2H8N2 (X = Cl, Br, I; Y = F, CN, NO2, LiNC+, NaNC+) Complex

Co-reporter:Na Han, Yanli Zeng, Xiaoyan Li, Shijun Zheng, and Lingpeng Meng

The Journal of Physical Chemistry A 2013 Volume 117(Issue 48) pp:12959-12968

Publication Date(Web):November 15, 2013

DOI:10.1021/jp408151t

Halogen-bonding interactions are highly directional intermolecular interactions that are often important in crystal engineering. In this work, the second-order Møller–Plesset perturbation theory (MP2) calculations and the quantum theory of “atoms in molecules” (QTAIM) and noncovalent 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 ρb, its Laplacian ∇2ρb, and −Gb/Vb of XB, indicating that the topological properties (ρb, ∇2ρb) and energy properties (Gb, Vb) at the BCPs are correlated with the electrostatic potentials.

Interplay between halogen bonds and hydrogen bonds in OH/SH···HOX···HY (X = Cl, Br; Y = F, Cl, Br) complexes

Co-reporter:Wenjie Wu;Yanli Zeng;Xiaoyan Li;Xueying Zhang

Journal of Molecular Modeling 2013 Volume 19( Issue 3) pp:1069-1077

Publication Date(Web):2013 March

DOI:10.1007/s00894-012-1657-z

The character of the cooperativity between the HOX···OH/SH halogen bond (XB) and the Y―H···(H)OX hydrogen bond (HB) in OH/SH···HOX···HY (X = Cl, Br; Y = F, Cl, Br) complexes has been investigated by means of second-order Møller−Plesset perturbation theory (MP2) calculations and “quantum theory of atoms in molecules” (QTAIM) studies. The geometries of the complexes have been determined from the most negative electrostatic potentials (VS,min) and the most positive electrostatic potentials (VS,max) on the electron density contours of the individual species. The greater the VS,max values of HY, the larger the interaction energies of halogen-bonded HOX···OH/SH in the termolecular complexes, indicating that the ability of cooperative effect of hydrogen bond on halogen bond are determined by VS,max of HY. The interaction energies, binding distances, infrared vibrational frequencies, and electron densities ρ at the BCPs of the hydrogen bonds and halogen bonds prove that there is positive cooperativity between these bonds. The potentiation of hydrogen bonds on halogen bonds is greater than that of halogen bonds on hydrogen bonds. QTAIM studies have shown that the halogen bonds and hydrogen bonds are closed-shell noncovalent interactions, and both have greater electrostatic character in the termolecular species compared with the bimolecular species.

Electron Structure of Arx′ZnZnArx′ (Arx′ = C6H3-2, 6-(C6H5)2) Determined from ELF and NBO Data: Effects of Hydrogen/Sodium Atoms on Zn–Zn Interactions

Co-reporter:Xiaoyan Li, Jie Sun, Zheng Sun, Yanli Zeng, Shijun Zheng, and Lingpeng Meng

Organometallics 2012 Volume 31(Issue 18) pp:6582-6588

Publication Date(Web):September 7, 2012

DOI:10.1021/om300587e

The nature of Zn–Zn bonding in Arx′ZnZnArx′ (Arx′ = C6H3-2,6-(C6H5)2)) was studied and was compared with the bonding in its derivatives Arx′Zn(μ-H)2ZnArx′, Arx′Zn(μ-H)(μ-Na)ZnArx′, and Arx′Zn(μ-Na)2ZnArx′; this study was carried out within the framework of the atoms in molecules (AIM) theory and using electron localization function (ELF) and natural bond orbital (NBO) analysis. The calculated results showed that, in Arx′ZnZnArx′, the Zn–Zn bond was stronger than a single bond; it was intermediate between a single and a double bond. Howerver, this bond was different from the classical single bond, in which the valence basin is concentrated tightly around the bond axis; in this case, the valence basin was in a toroidal configuration around the Zn–Zn bond, with axial symmetry. The Zn–Zn bond was weakened and its axial symmetry broken down when one or two hydrogen/sodium atoms were introduced to Arx′ZnZnArx′; the influence of a hydrogen atom was more pronounced than that of a sodium atom. It was shown that two Zn–H–Zn or Zn–Na–Zn three-center–two-electron (3c-2e) bridged bonds existed in Arx′Zn(μ-H)2ZnArx′, Arx′Zn(μ-H)(μ-Na)ZnArx′, and Arx′Zn(μ-Na)2ZnArx′. In the formation processes of these 3c-2e bridged bonds, the sodium atom acted as the electron donor, whereas the hydrogen atom acted as an electron acceptor.

Nature of Chemical Bonding and Metalloaromaticity of Na2[(MArx′)3] (M = B, Al, Ga; Arx′ = C6H3-2,6-(C6H5)2)

Co-reporter:Xiaoyan Li, Jie Sun, Yanli Zeng, Zheng Sun, Shijun Zheng, and Lingpeng Meng

The Journal of Physical Chemistry A 2012 Volume 116(Issue 22) pp:5491-5496

Publication Date(Web):May 21, 2012

DOI:10.1021/jp302780v

The nature of chemical bonding and metalloaromaticity of Na2[(MArx′)3] (M = B, Al, Ga) have been studied within the framework of the atoms in molecules (AIM) theory and using electron localization function (ELF) analysis. The π electrons of the studied systems were separated from the total electron density and analyzed. The calculated results indicate that there are closed-shell weak interactions between the sodium atom and the M3 (M = B, Al, Ga) ring, between the sodium atom and the terminal phenyl group on each Arx′, and between the terminal phenyl groups on Arx′ in Na2[(MArx′)3]. The Na2[(MArx′)3] has metalloaromatic nature, and the sodium atoms have an active role in determining the computed aromatic properties of the three-numbered cycle.

AIM and ELF Analyses of Halogen Bonding in NCS:BrCl Complexes

Co-reporter:Xiaoyan Li;Jie Sun;Xueying Zhang;Yanli Zeng;Shijun Zheng

Chinese Journal of Chemistry 2011 Volume 29( Issue 11) pp:2416-2420

Publication Date(Web):

DOI:10.1002/cjoc.201100055

Abstract

The nature of halogen bonding in five complexes formed between the thiocyanate (NCS) radical and a BrCl molecule was analyzed by quantum theory of atoms in molecules (QTAIM) and electron-localization function (ELF) in this paper. The calculated results show that the geometry of the halogen atom bonded at the N-atom is stable than those bonded at S- or C-atom. The molecular electrostatic potentials determine the geometries and stabilities of the complexes. The valence basin of the S- or N-atom in the electron-donating NCS radical is compressed and its population decreases during the process of formation of the halogen-bonded complexes.

Cooperativity between S···π and Rg···π in the OCS···C6H6···Rg (Rg = He, Ne, Ar, and Kr) van der Waals Complexes

Co-reporter:Yanli Zeng, Jing Hao, Shijun Zheng, and Lingpeng Meng

The Journal of Physical Chemistry A 2011 Volume 115(Issue 40) pp:11057-11066

Publication Date(Web):August 31, 2011

DOI:10.1021/jp206835m

The complexes OCS···C6H6, C6H6···Rg, and OCS···C6H6···Rg (Rg = He, Ne, Ar, and Kr) have been studied by means of MP2 calculations and QTAIM analyses. The optimized geometries of the title complexes have C6v symmetry. The intermolecular interactions in the OCS···C6H6···Rg complexes are comparatively stronger than that in the OCS···C6H6 complex, which prove that the He, Ne, Ar, and Kr atoms have the ability to form weak bonds with the benzene molecule. In QTAIM studies, the π-electron density of benzene was separated from the total electron density. The molecular graphs and topological parameters of the OCS···πC6H6, πC6H6···Rg, and OCS···πC6H6···Rg complexes indicate that the interactions are mainly attributed to the electron density provided by the π-bonding electrons of benzene and the top regions of the S and Rg atoms. Charge transfer is observed from the benzene molecule to SCO/Rg in the formation of the OCS···C6H6, C6H6···Rg, and OCS···C6H6···Rg complexes. Molecular electrostatic potential (MEP) analyses suggest that the electrostatic energy plays a pivotal role in these intermolecular interactions.

Insight into the lithium/hydrogen bonding in (CH2)2X...LiY/HY (X: C=CH2, O, S; Y=F, Cl, Br) complexes

Co-reporter:Xiaoyan Li;Yanli Zeng;XueYing Zhang;Shijun Zheng

Journal of Molecular Modeling 2011 Volume 17( Issue 4) pp:757-767

Publication Date(Web):2011 April

DOI:10.1007/s00894-010-0768-7

The nature of the lithium/hydrogen bonding between (CH2)2X(X: C=CH2, O, S) and LiY/HY(Y=F, Cl, Br) have been theoretically investigated at MP2/6-311++G (d, p) level, using Bader’s “atoms in molecules (AIM)” theory and Weinhold’s “natural bond orbital (NBO)” methodology. The molecule formation density differences (MFDD) of the titled complexes are analyzed. Two kinds of geometries of the lithium/hydrogen bonded complexes are compared. As a whole, the nature of lithium bond and hydrogen bond are different. For the same electron donor and the same acceptor, lithium bond is stronger than hydrogen bond. For the same electron acceptor and different kind of donors, the interaction energies follows the n-type> π-type > pseudo-π-type order. For the same (CH2)2X, the interaction energy increases in the sequence of Y=F, Cl and Br for lithium bond systems while it decreases for hydrogen bond systems. Electron transfer plays an important role in the formation of lithium bond systems while it is less important in the hydrogen bond systems.

Insight into the nature of the interactions of furan and thiophene with hydrogen halides and lithium halides: ab initio and QTAIM studies

Co-reporter:Yanli Zeng;Xiaoyan Li;Xueying Zhang;Shijun Zheng

Journal of Molecular Modeling 2011 Volume 17( Issue 11) pp:2907-2918

Publication Date(Web):2011 November

DOI:10.1007/s00894-011-0987-6

The nature of the interactions of furan and thiophene with hydrogen halides and lithium halides has been investigated using ab initio calculations and QTAIM analysis. The concept of molecule formation density difference (MFDD) is introduced to study weak hydrogen bond (HB) and lithium bond (LB) interactions. The results have shown the molecular electrostatic potentials of furan and thiophene, as well as of the hydrogen halides and lithium halides, determine the geometries of the complexes. Both the studied HB and LB interactions can be classified as “closed-shell” weak interactions. The topological properties and energy properties at the bond critical points of HB and LB have been shown to be exponentially dependent on intermolecular distances d(H-bond) and d(Li-bond), which enables interpretation of the strength of the HB and LB interactions in terms of these ρ(r) properties. Electron transfer plays a more important role in the formation of HB than in that of LB, while electrostatic interaction in LB is more dominant than that in HB.Table of Contents (TOC) Image

First-principles studies of the structures and properties of Al- and Ag-substituted Mg2Ni alloys and their hydrides

Co-reporter:Yanli Zeng, Ke Fan, Xiaoyan Li, Baoen Xu, Xiaozhen Gao, Lingpeng Meng

International Journal of Hydrogen Energy 2010 Volume 35(Issue 19) pp:10349-10358

Publication Date(Web):October 2010

DOI:10.1016/j.ijhydene.2010.07.131

The structures and properties of hydrogen storage alloy Mg2Ni, of aluminum and silver substituted alloys Mg2−xMxNi (M = Al and Ag, x = 0.16667), and of their hydrides Mg2NiH4, Mg2−xMxNiH4 (M = Al and Ag, x = 0.125) have been calculated from first-principles. Results show that the primitive cell sizes of the intermetallic alloys and hydrides were reduced by substitution of Mg with Al or Ag. Also, the interaction of Ni–Ni was weakened by the substitution. A strong covalent interaction between H and Ni atoms forms tetrahedral NiH4 units in Mg2NiH4. The NiH4 unit near the Al/Ag atom became tripod-like NiH3 in Mg2−xMxNiH4 (M = Al, Ag), indicating that the hydrogen storage capacity was decreased by the substitution. The calculated enthalpies of hydrogenation for Mg2Ni, Mg2−xAlxNi and Mg2−xAgxNi are −65.14, −51.56 and −53.63 kJ/mol H2, respectively, implying that the substitution destabilizes the hydrides. Therefore, the substitution is an effective technique for improving the thermodynamic behavior of hydrogenation/dehydrogenation in magnesium-based hydrogen storage materials.

AIM studies on SSHX → HSSX (X = F, Cl, Br, I) reaction

Co-reporter:Yanli Zeng, Xiaoyan Li, Xueying Zhang, Shijun Zheng, Lingpeng Meng

Journal of Molecular Structure: THEOCHEM 2008 Volume 851(1–3) pp:115-120

Publication Date(Web):28 February 2008

DOI:10.1016/j.theochem.2007.11.011

The reactions of SSHX to HSSX (X = F, Cl, Br and I) have been studied at the MP2/6-311++G(2df,pd)//B3LYP/6-311++G(2df,pd) level. The SSH and SSX ring structure transition region (STR) and respective structure transition state (STS) have been studied in the framework of the “Atoms in Molecules” theory. The following conclusions are drawn: (a) For the SSH and SSX ring structures, according to the sequence of X = F, Cl, Br and I, the STR becomes broader and the STS appears later. (b) For the H atom transfer pathway and X atom transfer pathway, the lower the energy barrier is, the broader the ring STR (SSH ring STR or SSX ring STR) is and the later the STS appears.

Influences of the substituents on the M–M bonding in Cp4Al4 and Cp2M2X2 (M = B, Al, Ga; Cp = C5H5, X = halogen)

Co-reporter:Feifei Lu, Xiaoyan Li, Zheng Sun, Yanli Zeng and Lingpeng Meng

Dalton Transactions 2015 - vol. 44(Issue 31) pp:NaN14100-14100

Publication Date(Web):2015/06/30

DOI:10.1039/C5DT01901J

Enhancing σ/π-type copper(I)⋯thiophene interactions by metal doping (metal = Li, Na, K, Ca, Sc)

Co-reporter:Xiayan Zhang, Xiaoyan Li, Yanli Zeng, Shijun Zheng and Lingpeng Meng

Dalton Transactions 2015 - vol. 44(Issue 3) pp:NaN1291-1291

Publication Date(Web):2014/10/15

DOI:10.1039/C4DT02286F