We designed three novel cage energetic anions by introducing ionic bridges containing NΘ, N(OΘ) and N(NΘNO2) into cis-2,4,6,8-tetranitro-1H,5H-2,4,6,8- tetraazabicyclo[3.3.0] octane (bicyclo-HMX or BCMHX). The properties of 21 energetic salts, based on cage anions and ammonium-based cations, were studied by density functional theory (DFT) and volume-based thermodynamics (VBT) calculations. Compared to the parent nonionic BCHMX, most title salts have lower predicted impact sensitivities, higher predicted densities, larger predicted heats of formation (HOFs) and better predicted detonation properties. In particular, 11 energetic salts not only exhibit excellent predicted energetic properties, superior to 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20), but also have lower predicted sensitivity than CL-20. The best salt had a predicted detonation velocity of 10.06 km s?1, a predicted detonation pressure of 48.54 GPa and a predicted sensitivity (h50) of 23.99 cm. By introducing ionic bridges into highly nitrated rings, or modifying the original bridge with ionic bridges, some highly nitrated cage compounds with both excellent performance and low sensitivity can be developed strategically.
The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in methanol, water, and chloroform in the molecularly imprinted recognition were investigated systematically. The M06-2X results revealed that: 1) the hydroxyl groups in polar solvents such as methanol and water may markedly influence the weak interactions, and then alter the adsorption and emission spectra; 2) the electronic excitation in absorption spectra of dichlorvos is dominated by the configuration HOMO?→?LUMO, but in the most stable dichlorvos-MAA it becomes the ππ* excitation of HOMO?→?LUMO?+?1; 3) Mulliken charges reveal that dichlorvos almost dissociates to Cl- and a cation in its S1 excitation state; 4) the phosphorescence spectra of dichlorvos-MAA are relatively weak.
Graphical Abstract The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in the molecularly imprinted recognition of dichlorvos were investigated systematically in methanol, water, and chloroform as solvents.
Mechanisms for the activation of water, ammonia, and other small molecules by the PCcarbeneP nickel pincer complex were studied computationally with the aid of density functional theory. The calculation results indicate that the strongly donating, nucleophilic carbene center can engage in a variety of heterolytic splitting of E?H (E=H, C, N, O) bonds, some of which are reversible. The cleavage of E?H bonds across the Ni=C bond represents a new mode of bond activation by ligand cooperativity in nickel pincer complex. On the basis of the calculations, we also demonstrate that reversible H2 activation across the Ir=C bond via the PCcarbeneP iridium pincer complex was observed in the experiments, while other E?H (E=C, N, O) bonds were not activated. Our calculations are in good agreement with experimental observations and could provide new insights into ligand cooperativity in nickel pincer complexes.
MP2/aug-cc-pVTZ calculations were performed for complexes linked by hydrogen bonds. Three types of proton donating species were taken into account: H2O, CCl3H, and H3O+. These calculations are supported by the natural bond orbital (NBO) method and the quantum theory of atoms in molecules (QTAIM) approach. Numerous correlations between parameters of H-bonded systems were found. The most important are those which show the response of the system on the H-bond formation; for example, the increase of polarization of the A-H bond correlates with the strength of the hydrogen bond. Similar relationships were found for the σ-hole bonds while the π-hole bonds do not follow the trends known for the hydrogen bonds.
Protonation in the two-electron/two-proton reduction processes of 2,6-dichlorophenolindophenolate (DCIP) is investigated combining density functional theory (DFT) and molecular dynamics (MD) methods. DCIP (anion), DCIP?– (radical anion), and DCIP2? (dianion) are considered, including the electronic structure analysis from the prospective of quantum theory of atoms and molecules (QTAIM). It is shown that oxygen on the indophenolate moiety and nitrogen are the first and/or the second proton acceptor sites and their energetic order depends on the total charge of the system. MD simulations of differently charged species interacting with the solvent molecules have been performed for methanol, water, and oxonium cation (H3O+). Methanol and water molecules are found to form only hydrogen bonds with the solute irrespective of its charge. The calculated pKa values show that the imino group of DCIPH? is a weaker acid than water. While in the case of DCIP (and DCIP?–) plus oxonium cation, proton transfer from the solvent to the solute was evidenced for both aforementioned acceptor sites. In addition, MD simulations of bulks containing 15 and 43 molecules of water around the DCIP molecule have been performed, revealing the formation of 2–4 hydrogen bonds.
Graphical Abstract 2,6-Dichlorophenolindophenolate interacts with solvent molecules (water, oxonium cation and methanol). Hydrogen transfer and electronic structure are studied by DFT and molecular dynamics methods
A dispersion correction is introduced and tested for MNDO. The shift in electron density caused by the interaction between oscillating dipoles in the London picture of dispersion is mimicked by adding a small r?7-dependent attractive nucleus–electron potential to the core Hamiltonian. This potential results in a shift in electron density similar to that used by Feynman to explain dispersion. The resulting parameterized self-consistent and inherently multicenter treatment (MNDO-F) gives good results for CHNO compounds that do not exhibit hydrogen bonds, which MNDO cannot reproduce. This “Feynman” dispersion correction is also applicable to Hartree–Fock and density functional theory.
An accurate comparison of the interaction of furan, pyrrole, and thiophene with different gaseous analytes is vital not only for understanding the sensing mechanism of corresponding polymers but also for rational design of new materials. In the present study, DFT calculations at (M05-2X/Aug-cc-PVDZ) have been performed to investigate the interaction behavior of furan, pyrrole, and thiophene (as models for their corresponding polymers) with different analytes (NH3, CO2, CO, N2H4, HCN, H2O2, H2S, CH4, CH3OH, SO2, SO3, H2O). The interaction of heterocycles with analytes is illustrated by changes in geometric, energetic, and electronic properties. SAPT calculations were performed for energy decomposition analysis to study the contribution of non-covalent components of the total interaction energy for each complex. Analysis of energetic and electronic properties reveals that all heterocycles are highly sensitive to SO3. The results suggest that sensing ability of polypyrrole is higher than polyfuran and polythiophene for all analytes.
The nature of M–M bonding and aromaticity of [M2(NHCHNH)3]2(μ-E)2 (E?=?O, S; M?=?Nb, Mo, Tc, Ru, Rh) was investigated using atoms in molecules (AIM) theory, electron localization function (ELF), natural bond orbital (NBO) and molecular orbital analysis. These analyses led to the following main conclusions: in [M2(NHCHNH)3]2(μ-E)2 (E?=?O, S; M?=?Nb, Mo, Tc, Ru, Rh), the Nb–Nb, Ru–Ru, and Rh–Rh bonds belong to “metallic” bonds, whereas Mo–Mo and Tc–Tc drifted toward the “dative” side; all these bonds are partially covalent in character. The Nb–Nb, Mo–Mo, and Tc–Tc bonds are stronger than Ru–Ru and Rh–Rh bonds. The M–M bonds in [M2(NHCHNH)3]2(μ-S)2 are stronger than those in [M2(NHCHNH)3]2(μ-O)2 for M?=?Nb, Mo, Tc, and Ru. The NICS(1)ZZ values show that all of the studied molecules, except [Ru2(NHCHNH)3]2(μ-O)2, are aromaticity molecules. O-bridged compounds have more aromaticity than S-bridged compounds.
Graphical AbstractLeft Molecular graph, and right electron localization function (ELF) isosurface of [M2(NHCHNH)3]2(μ-E)2(E?=?O, S; M?=?Nb, Mo, Tc, Ru, Rh)
In this article, we explore the capacity of formed Schiff base complexes to trap metal atoms or ions, using their aromatic ends. The intrinsic geometry of each complex defines the process of substitution. Two cases were studied; one involving a trans Schiff base complex and the other considering how a salen ligand, with nickel systems traps chromium. We also assessed the nature of the new bonds and the frontier molecular orbitals.
The main purpose of this study was to address the performance of virtual screening methods based on ligands and the protein structure of acetylcholinesterase (AChE) in order to retrieve novel human AChE (hAChE) inhibitors. In addition, a protocol was developed to identify novel hit compounds and propose new promising AChE inhibitors from the ZINC database with 10 million commercially available compounds. In this sense, 3D similarity searches using rapid overlay of chemical structures and similarity analysis through comparison of electrostatic overlay of docked hits were used to retrieve AChE inhibitors from collected databases. Molecular dynamics simulation of 100 ns was carried out to study the best docked compounds from similarity searches. Some key residues were identified as crucial for the dual binding mode of inhibitor with the interaction site. All results indicated the relevant use of EON and docking strategy for identifying novel hit compounds as promising potential anticholinesterase candidates, and seven new structures were selected as potential hAChE inhibitors.
Seven models that related the features of molecular surface electrostatic potentials (ESPs) above the bond midpoints and rings, statistical parameters of ESPs to the experimental impact sensitivities h50 of eight strained cyclic explosives with the C–NO2 bonds were theoretically predicted at the DFT-B3LYP/6-311++G** level. One of the models was used to investigate the changes of h50 for the nitrocyclohydrocarbon frameworks in the H-bonded complexes of HF with nitrocyclopropane, nitrocyclobutane, nitrocyclopentane, and nitrocyclohexane. The results show that the correlation coefficients of the obtained models are small. When adding the effect of ring strain, the value of correlation coefficient is increased. According to the calculated h50, the sensitivities in the frameworks are increased after hydrogen bonding. As a global feature of molecules, surface electrostatic potential is more available to judge the sensitivity change than the trigger bond dissociation energy or ring strain energy in H-bonded complex.
Graphical Abstract A theoretical prediction of the relationships between the impact sensitivity and electrostatic potential in strained cyclic explosive and application to H-bonded complex of nitrocyclohydrocarbon?
The correlation between the kinetic stability of molecules against temperature and variations in their geometric structure under optical excitation is investigated by the example of different organic pheromone molecules sensitive to temperature or ultraviolet radiation using the density functional theory. The kinetic stability is determined by the previously developed method based on the calculation of the probability of extension of any structural bond by a value exceeding the limit value Lмах corresponding to the breaking of the bond under temperature excitation. The kinetic stability calculation only requires the eigenfrequencies and vibrational mode vectors in the molecule ground state to be calculated, without determining the transition states. The weakest bonds in molecules determined by the kinetic stability method are compared with the bond length variations in molecules in the excited state upon absorption of light by a molecule. Good agreement between the results obtained is demonstrated and the difference between them is discussed. The universality of formulations within both approaches used to estimate the stability of different pheromone molecules containing strained cycles and conjugated, double, and single bonds allows these approaches to be applied for studying other molecules.
In this work, six (A–F) nitramino (–NHNO2)-substituted ditetrazole 2-N-oxides with different bridging groups (–CH2–, –CH2–CH2–, –NH–, –N=N–, and –NH–NH–) were designed. The six compounds were based on the parent compound tetrazole 2-N-oxide, which possesses a high oxygen balance and high density. The structure, heat of formation, density, detonation properties (detonation velocity D and detonation pressure P), and the sensitivity of each compound was investigated systematically via density functional theory, by studying the electrostatic potential, and using molecular mechanics. The results showed that compounds A–F all have outstanding energetic properties (D: 9.1–10.0 km/s; P: 38.0–46.7 GPa) and acceptable sensitivities (h50: 28–37 cm). The bridging group present was found to greatly affect the detonation performance of each ditetrazole 2-N-oxide, and the compound with the –NH–NH– bridging group yielded the best results. Indeed, this compound (F) was calculated to have comparable sensitivity to the famous and widely used high explosive 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), but with values of D and P that were about 8.7% and 19.4% higher than those for HMX, respectively. The present study shows that tetrazole 2-N-oxide is a useful parent compound which could potentially be used in the design of new and improved high-energy compounds to replace existing energetic compounds such as HMX. 相似文献
4-[N-(2-cyanoethyl)-N-ethylamino]-4′-nitroazo-benzene (disperse orange 25, DO25) is one of the main components in dyeing wastewater. In this work, supercritical water oxidation (SCWO) process of DO25 has been investigated using the molecular dynamic simulations based on the reactive force field (ReaxFF). For the SCWO system, the effects of temperature, the molecular ratio of DO25, O2 and H2O as well as the reaction time have been analyzed. The simulated results showed that the aromatic rings in DO25 could be attacked by hydroxyl radical, oxygen molecule, and hydroxyl radical together with oxygen molecule, respectively, which caused the aromatic ring-opening reaction to happen mainly through three different pathways. The hydroxyl radicals were mainly from water clusters and H2O2 (which was produced from oxygen molecules reacting with water clusters). However, for the SCW system as comparison, the aromatic rings in DO25 could be attacked by hydroxyl radical only, and the OH radicals just come from water clusters. During the DO25 SCWO degradation process, we also found that N elements in one DO25 molecule were difficult to be converted into environmentally friendly N2 molecules because of steric hindrance, but increasing the number of DO25 molecules could improve the possibility for the connection of N elements, thus promoting N element converting into N2. Extending reaction time could also improve N elements in DO25 to transform into N2 rather than carbonitride.
Magnetic shielding constants for an isolated fullerene C60, cucurbituril CB[9], and the host-guest complex C60@CB[9] were calculated as a function of separation of the monomers. Our results in the gas phase and water indicate a significant variation of the magnetic properties for all atoms of the monomers in the complex and after liberation of fullerene C60 from the interior of the CB[9] cavity. The interaction between the two monomers results in a charge transfer that collaborates with a redistribution of electron density to deshield the monomers.
Utilizing first-principles calculations, we studied the electronic and optical properties of C24, C12X6Y6, and X12Y12 fullerenes (X?=?B, Al; Y?=?N, P). These fullerenes are energetically stable, as demonstrated by their negative cohesive energies. The energy gap of C24 may be tuned by doping, and the B12N12 fullerene was found to have the largest energy gap. All of the fullerenes had finite optical gaps, suggesting that they are optical semiconductors, and they strongly absorb UV radiation, so they could be used in UV light protection devices. They could also be used in solar cells and LEDs due to their low reflectivities.
Detailed electrostatic potential (ESP) analyses were performed to compare the directionality of halogen bonds with those of hydrogen bonds and lithium bonds. To do this, the interactions of HOOOH with the molecules XF (X?=?Cl, Br, H, Li) were investigated. For each molecule, the percentage of the van der Waals (vdW) molecular surface that intersected with the ESP surface was used to roughly quantify the directionality of the halogen/hydrogen/lithium bond associated with the molecule. The size of the region of intersection was found to increase in the following order: ClF?<?BrF?<?HF?<?LiF. The maximum ESP in the region of intersection, VS, max, was observed to become more positive according to the sequence ClF?<?BrF?<?HF?<?LiF. For ClF and BrF, the positive electrostatic potential was concentrated in a very small region of the vdW molecular surface. On the other hand, for HF and LiF, the positive electrostatic potential was more diffusely scattered across the vdW surface than for ClF and BrF. Also, the optimized geometries of the dipolymers HOOOH···?XF (X?=?Cl, Br, H, Li) indicated that halogen bonds are more directional than hydrogen bonds and lithium bonds, consistent with the results of ESP analyses.
The effect of alkali metal oxides MnO (M?=?Li, Na, K; n?=?2, 3, 4) on the geometric, electronic, and linear and nonlinear optical properties of the Mg12O12 nanocage was investigated by density-functional-based methods. According to the computational results, these alkali metal oxides are adsorbed on the Mg12O12 nanocage because this adsorption reduces its energy gap. The static first hyperpolarizability (β0) of the nanocage is dramatically increased in the presence of the alkali metal oxides, with the greatest increase seen in the presence of the superalkalis (i.e., M3O; M?=?Li, Na, and K). The highest first hyperpolarizability (β0?≈?600,000 a.u.) was calculated for K3O@Mg12O12, which was considerably more than that for Mg12O12. The thermodynamic properties and relative stabilities of these inorganic compounds are discussed.
