Theoretical study of cooperativity between hydrogen bond‒hydrogen bond,halogen bond‒halogen bond and hydrogen bond‒halogen bond in ternary FX…diazine…XF (X = H and Cl) complexes

ABSTRACT

In the present work, the cooperativity between hydrogen bond?hydrogen bond, halogen bond?halogen bond and hydrogen bond?halogen bond in ternary FX…diazine…XF (X = H and Cl) complexes is theoretically investigated. The sign of cooperative energy (E_coop) obtained in all of the triads is positive which indicates that the ternary complex is less stable than the sum of the two isolated binary complexes. Moreover, our calculations show that E_coop value in triads increases as FX…pyridazine…XF > FX…pyrimidine…XF > FX…pyrazine…XF. In agreement with energetic, geometrical and topological properties, electrostatic potentials and coupling constants across ¹⁵N…X?¹⁹F (X = ¹H or ³⁵Cl) hydrogen and halogen bonds indicate that hydrogen and halogen bonds are weakened in the considered complexes where two hydrogen and halogen bonds coexist. As compared to N…H hydrogen bond, it is also observed that cooperativity has greater effect on N…Cl halogen bond.     

A-dependence of ΛΛ bond energies in double-Λ hypernuclei

The A-dependence of the bond energy ΔB_ΛΛ of the ΛΛ hypernuclear ground states is calculated in a three-body Λ + Λ + ^A Z model and in the Skyrme-Hartree-Fock approach. Various ΛΛ and Λ-nucleus or ΛN potentials are used and the sensitivity of ΔB_ΛΛ to the interactions is discussed. It is shown that in medium and heavy ΛΛ hypernuclei, ΔB_ΛΛ is a linear function of r _Λ ^{? 3} , where r _Λ is rms radius of the hyperon orbital. It looks unlikely that it will be possible to extract ΛΛ interaction from the double-Λ hypernuclear energies only, the additional information about the Λ- core interaction, in particular, on r _Λ is needed.     

Double heavy tri-hadron bound state via delocalized π bond

The number of exotic candidates that are beyond the conventional quark model has increased dramatically over recent decades.Some of these can be viewed as analogues of the deuteron.Similarly,the existence of the triton indicates that bound states formed by three hadrons could also exist.To illustrate this possibility,we study the DD~*K and■systems using the Born-Oppenheimer approximation.To leading order,only one-pion exchange potentials are considered.This means that the three constituents share one virtual pion.This is similar to the role of the delocalizedπbond for the formation of benzene in chemistry.After solving the Schr?dinger equation,we find two three-body DD~*K and■ bound states with masses 4317.92~_(-6.55)(+6.13)Me V and11013.65_(-8.84)~(+8.49)Me V,respectively.The masses of their ■and■ analogues are 4317.92~_(-6.55)(+6.13)Me V and11013.65_(-9.02)~(+8.68)Me V,respectively.From the experimental side,the ■bound state could be found by analyzing the current world data on the B→J/ψππKprocess,by focusing on the J/ψπK channel.     

On difference of properties between organic fluorine hydrogen bond C–H···F–C and conventional hydrogen bond

The existence of C–H···F–C hydrogen bonds in the complexes of trifluoromethane and cyclic molecule (oxirane, cyclobutanone, dioxane, and pyridine) has been experimentally proven by Caminati and co-workers. This study presents a theoretical investigation on these C–H···F–C hydrogen bonds at B97D/6-311++G^** and MP2/6-311++G^** levels, in terms of C–H vibrational frequency shifts, atoms in molecules characteristics, and the bonding feature of C–H···F–C hydrogen bonds. It is found that in three important aspects, there are significant differences in properties between C–H···F–C and conventional hydrogen bonds. The C–H···F–C hydrogen bonds show a blueshift in the C–H vibrational frequencies, instead of the X–H normal redshift in X–H···Y conventional hydrogen bonds. The natural bond orbital (NBO) analyses show that σ and p types of lone pair orbitals of the F atom to an antibonding σ^*_H–C orbital form a dual C–H···F–C hydrogen bond. Such a dual hydrogen bonding leads to the proton acceptor directionality of the C–H···F–C hydrogen bond softer. Our studies also show that the Laplacian of the electron density (▽²ρ_BCP) is not always a good criterion for hydrogen bonds. Therefore, we should not recommend the use of the Laplacian of the electron density as a criterion for C–H···F–C hydrogen bonds.     

The strong OHO hydrogen bond. How much covalency?

In the strong OHO hydrogen bond of the phosphoric acid–urea 1?:?1 complex the proton shifts gradually with temperature from the donor towards the acceptor atom, passing through the center of the hydrogen bond at around 315?K. The AIM parameters were evaluated for the published neutron structures at different temperatures. The values of the electron density, its Laplacian, and the energy densities at both the critical points between the proton and the oxygen atoms in the OHO hydrogen bond were correlated with the OH and HO distances. Changes in the AIM parameters of the strong hydrogen bond were compared with those of the weak NHO bond in this complex.     

Delocalized π state between molecules through a surface confined pseudodihydrogen bond

When 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) and coronene molecules coadsorb on the Ag(111) surface, one-dimensional PTCDA molecular oligomers with efficient electronic connection via noncovalent bonds are observed by low temperature scanning tunneling microscopy. Density functional theory calculations indicate the neighboring PTCDA molecules form oligomers due to strong PTCDA-metal interactions, which result in overlapping of π orbitals and pseudodihydrogen surface bonds between molecules. Our results provide a potential approach for electron transport from molecule to molecule directly through noncovalent bond.     

‘True’ self-avoiding walks with generalized bond repulsion on ℤ

We consider a nearest-neighbor random walk on , for which the probability of jumping along a bond of the lattice is proportional to exp[–g. (number of previous jumps along that bond) ^k ], withg>0,k(0,1]. After a review of earlier results obtained for the casek=1 we outline the generalizations fork(0,1), obtaining a whole range of anomalous diffusion limits.Dedicated to Oliver Penrose on the occasion of his 65th birthday     

A first-principles investigation into the hydrogen bond interaction in β-HMX

A theoretical study of structural and electronic properties of β-HMX crystal is performed using density-functional theory(DFT). The total density of states(TDOS) is presented. The atomic orbit projected density of state(PDOS) from the p-type orbit of C,N,O and the s-type orbit of H is discussed. The study by analyzing the PDOS shows that the structure of β-HMX crystal possesses C-H···O intra- and inter-molecular hydrogen-bonding. There exists a hydrogen bonding between H5 -1s and O12 -2p orbits,between H19 -1s and O28 -2p orbits of intra molecules,and between H19 -1s and O24 -2p orbits of inter molecules. The Mulliken population analysis is also made.     

Preferential etching of Si–Si bond in the microcrystalline silicon germanium

Hydrogenated microcrystalline silicon germanium (μc-Si_1?xGe_x:H) films were investigated as a bottom cell absorber in multi-junction solar cells. μc-Si_1?xGe_x:H films were prepared using very high frequency (VHF, 60 MHz) plasma enhanced chemical vapor deposition (PECVD) systems working pressure of about 1.5 Torr. The precursor flow rates were carefully controlled to determine the phase transition point and to improve the crystallinity of μc-Si_1?xGe_x:H. A relatively high plasma power was necessary to have the high hydrogen (H₂) dilution. Raman spectroscopy study showed transition steps from amorphous to microstructure morphology as hydrogen dilution increasing. Crystallite Si–Ge and Ge–Ge bonds were occurred at relatively higher H₂ dilution compare to crystallite Si–Si bond. The rapidly increased Ge content as increasing the H₂ dilution is believed mainly due to the different decomposition rate of silane (SiH₄) and germane (GeH₄). The other reason of high Ge content even at the low GeH₄ precursor flow rate is probably due to the preferential etching of silicon atom by H₂. The preferential etching of Si–H possibly occurred in very highly concentrated H₂ plasma due to the preferential attachment of Si–H. The compositions of μc-Si_1?xGe_x:H films measured using RBS were Si_0.83Ge_0.17, Si_0.67Ge_0.33 and Si_0.59Ge_0.41 at H₂/SiH₄ flow rate of 60, 80 and 100, respectively. μc-Si_1?xGe_x:H films showed the dark (σ_d) and photo conductivity (σ_p) of about 10^?7 and 10^?5 S/cm, respectively and photo response (σ_p/σ_d) was about 10². This study will present the comprehensive evaluation of crystallization behavior of μc-Si_1?xGe_x:H films.     

Can 2‐acylpyrroles form an intramolecular hydrogen bond?

The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities H_BCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes ν_{C = O}, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the ν_C–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd.     

Hydrogen bond lifetimes in supercritical methanol–water mixtures via MD simulation

Dynamical features of hydrogen bonds in methanol–water mixtures have been analysed in terms of lifetime in the wide range of conditions, including supercritical states, using a molecular dynamics simulation with flexible potential models. Hydrogen bond characteristics in methanol–water mixtures were investigated by considering the combination of molecular species and donor–acceptor of hydrogen-bonded molecules. The hydrogen bond lifetimes mainly depend on temperature, and those in supercritical condition were about 1/10th of that at ambient condition. Focusing on the composition dependence of the hydrogen bond lifetime, the unique behaviour of that resulting from hydration structure was observed. Moreover, the molecular combination, which showed the largest hydrogen bond lifetime, was different for ambient and high temperature and high pressure conditions. The relationship between hydrogen bond lifetime and molar volume was also calculated to discuss the hydrogen bond lifetime in terms of the collision frequency of molecules and the intermolecular distance.     

The triel bond: a potential force for tuning anion–π interactions

Using ab-initio calculations, the mutual influence between anion–π and B···N or B···C triel bond interactions is investigated in some model complexes. The properties of these complexes are studied by molecular electrostatic potential, noncovalent interaction index, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. According to the results, the formation of B···N or B···C triel bond interactions in the multi-component systems makes a significant shortening of anion–π distance. Such remarkable variation in the anion–π distances has not been reported previously. The strengthening of the anion–π bonding in the multi-component systems depend significantly on the nature of the anion, and it becomes larger in the order Br^? > Cl^? > F^?. The parameters derived from the QTAIM and NBO methodologies are used to study the mechanism of the cooperativity between the anion–π and triel bond interactions in the multi-component complexes.     

Ion source effect on the bond length of ^4HeH^＋

The bond length of ^4HeH^＋ resulting from collision-induced destruction is measured at 1.4420 MeV using the Coulomb Explosion Technique. The measured bond length of ^4HeH^＋ is 0.094±0.003nm. The bond length of ^4HeH^＋ obtained with our radio frequency （RF） ion source is larger than that obtained with a duoplasmatron ion source at Argonne National Laboratory （ANL）, but the bond lengths of H^＋2 and H^＋3obtained separately by ANL and by us with the two different ion sources are consistent with each other, which implies that there exists an ion source effect on the bond length of ^4HeH^＋. The main reason why the 4^4HeH^＋ bond lengths obtained by the two different ion sources are different is also discussed.     

Competition between hydrogen bond and σ-hole interaction in SCS-HArF and SeCSe-HArF complexes

A computational study of the complexes formed between HArF and XCX (X?=?O, S, and Se) has been performed at the MP2/aug-cc-pVTZ level. Two types of complexes were found. One is formed through a hydrogen bond with XCX as the electron donor and the other is formed through the σ-hole interaction with XCX as the electron acceptor. The OCO-FArH complex is more stable than the OCO-HArF complex, whereas the XCX-HArF (X?=?S and Se) complex is more stable than the XCX-FArH complex. The distant H-Ar bond is shortened and exhibits a blue shift, but the associated one displays a red shift in SCS-HArF and SeCSe-HArF complexes. When compared with XCX-HF complex, the structure of the complex suffers a great effect from the inserted noble gas atom. The natural bond orbital (NBO) and atoms in molecules (AIM) have been performed for a better understanding of the interactions.     

Gold–sulfur bond breaking in Zn(II) tetraphenylporphyrin molecular junctions

Quantized conductance measured from single tetraphenylporphyrin molecules with and without a central zinc(II) [Zn(II)] atom was measured using a molecular break junction (MBJ) method. From the conductance histograms we observed an additional 1.7 Å stretch for two-state conductance in a single Zn(II) tetraphenylporphyrin (ZnTPP) molecule as compared to single state conductance in a free tetraphenylporphyrin (TPP) molecule, i.e., no central Zn(II) atom. First-principles density functional calculations, using an electrode–molecule–electrode model, are completed to provide insight into the mechanisms attributed to bond stretching, and eventual bond breaking, to better understand the additional 1.7 Å of stretching observed with ZnTPP.     

Two-dimensional mixed spin Ising models with bond dilution and random ±J interactions

Using the finite cluster approximation we study a mixed spin model (spins =1/2 andS=1) on a square lattice with nearest-neighbour and crystal field interactions. The nearest-neighbour couplingsK _ij are assumed to be independent random variables with distribution,P(K _ij )=p(K _ij –K)+(1–p)(K _ij –K), whereK>0. We investigate the cases =0 and =–1 corresponding to bond dilution and to random ±J interactions, respectively. In certain ranges ofp the phase diagrams exhibit tricritical behaviour and reentrance.Supported by the agreement of cooperation between the DFG and the CNR-MarocOn leave from Faculté des Sciences I, Université Hassan II, Casablanca, Morocco; and Laboratoire de Magnétisme Université de Rabat, Morocco     

Competition between σ-hole pnicogen bond and π-hole tetrel bond in complexes of CF2=CFZH2 (Z = P,As, and Sb)

ABSTRACT

A computational study of the complexes formed by F₂C=CFZH₂ (Z?=?P, As, and Sb) and F₂C=CFPF₂ with two Lewis bases (NH₃ and NMe₃) has been carried out. In general, two minima complexes are found, one with a σ-hole pnicogen bond and the other one with a π-hole tetrel bond in most complexes but two σ-hole pnicogen bonded complexes are obtained for F₂C=CFZH₂ and NH₃. They have similar stability though F₂C=CFSbH₂ engages in a much stronger σ-hole pnicogen bond with NMe₃. The –PF₂ substitution makes the π-hole on the terminal carbon form a tetrel bond with NH₃. A heavier –ZH₂ group engages in a stronger σ-hole pnicogen bond but results in a weaker π-hole tetrel bond. Other than electrostatic interaction, the stability of both complexes is attributed to the charge transfer from the N lone pair into the C–Z/H–Z anti-bonding orbital in the pnicogen bond and the C=C anti-bonding orbital in the tetrel bond.

The σ-hole pnicogen bonded and π-hole tetrel bonded complexes between F₂C=CFZH₂ (Z = P, As, and Sb) and two Lewis bases (NH₃ and NMe₃) have been compared. The results indicate that both interactions can compete, dependent on the nature of the N base.     

Electron density characteristics and charge transfer effect of hydrogen bond O–H···Pt(II): atoms in molecules study and natural bond orbital analysis

In this report, we extended the works of Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] on the nature of O–H···Pt hydrogen bond in trans-[PtCl₂(NH₃)(N–glycine)]·H₂O(1·H₂O) complex, by computational study of O–H···Pt interaction in [NBu₄][Pt(C₆F₅)₃(8-hydroxyquinaldine)], with emphasis on charge transfer effect in this interaction of platinum(II) and hydrogen atom. According to the crystallographic geometry reported by José María Casas et al., [NBu₄][Pt(C₆F₅)₃(8-hydroxyquinaldine)] possesses one O–H···Pt hydrogen bridging interaction, similar to the case in trans-[PtCl₂(NH₃)(N–glycine)]·H₂O(1·H₂O) complex. On the basis of topological criteria of electron density, we characterised this O–H···Pt interaction. Charge transferred between platinum(II) and σ^*_O–H orbital in this complex was calculated by using NBO method. The stabilised energy associated to charge transfer was estimated using a direct proportionality, that is 2–3 eV per electron transferred. Charge transfer effects in O–H···Pt hydrogen bonds were studied for these two complexes. Our results indicate that the interaction of O–H···Pt is closed–shell in nature with significant charge transfer, and that charge transfer effect is not negligible in the interaction of O–H···Pt. The second conclusion is different from the result of Rizzato et al.     

The strengthening effect of a hydrogen or lithium bond on the Z···N aerogen bond (Z = Ar,Kr and Xe): a comparative study

An ab initio study is performed on O₃Z···NCM···NCX (Z = Ar, Kr and Xe; M = H and Li; X = H, F and CH₃) complexes to investigate cooperativity effects between aerogen and hydrogen or lithium bonding interactions in these systems. To understand the cooperative effects, a detailed analysis of the binding distances, interaction energies and bonding properties is performed on these complexes. The results indicate that all Z···N and H/Li···N binding distances in the ternary complexes are shorter than those of corresponding binary systems. For a given M or X, cooperative energies increase as Z = Xe > Kr > Ar. Moreover, O₃Z···NCLi···NCX complexes exhibit a larger cooperative energy than O₃Z···NCH···NCX ones. The non-covalent interaction (NCI) index analysis indicates that the formation of an H/Li···N interaction in the ternary complexes shifts the location of the spike associated with the Z···N interaction towards the negative λ₂ρ values. This indicates that NCI analysis can be regarded as a useful tool for the study of cooperative effects between two different non-covalent interactions. Also, cooperative effects in O₃Z···NCM···NCX complexes make a decrease in ¹⁴N nuclear quadrupole coupling constants of NCH or NCLi molecule.