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1.
The dissociation of O2 and HO2 are important reactions that occur at the cathode of fuel cells and require catalysts to proceed. There is a need to replace the presently used platinum catalyst with less expensive materials. Modelling has been used to identify potential two-dimensional catalysts such as boron- and nitrogen-doped graphene. Here, the possibility of boron nitride nano-ribbons and nano-tubes which do not require doping are considered. Density functional calculations are used to show that O2 and HO2 can bond to zig–zag and armchair boron nitride nano-ribbons and nano-tubes. The bond dissociation energies (BDEs) to remove an O and an OH from O2 and HO2 bonded to the boron nitride ribbons and tubes are calculated and are a measure of the catalytic effectiveness of the boron nitride structures. The results show that both the zig–zag and armchair boron nitride ribbons could be a catalyst for HO2 dissociation but not O2 dissociation. However, zig–zag boron nitride nano-tubes are shown not to be effective catalysts for the dissociation of O2 or HO2. An armchair boron nitride nano-tube is shown to have a very low BDEs to remove OH from HO2 bonded to it and could be an affective catalyst.  相似文献   

2.
Abstract

Introduction

A new method for calculating theoretical bond dissociation enthalpy (BDE) and bond dissociation free energy (BDFE) of hydroxylic antioxidants is forwarded. BDE and BDFE may be understood as activation energies accompanying the formation of transition states, which may undergo downhill homolytic dissociation. The new method does not involve the complete fission of O–H bonds.

Method

Theoretical gas phase BDE values were calculated with the ab initio unrestricted Hartree–Fock (UHF) method, as changes in enthalpy between ground singlet states (GS) and triplet dissociative states (DS). Similarly, gas phase BDFEs were estimated from the corresponding changes in Gibbs free energy. The results were then compared with reliable experimental reports.

Results

The proposed theoretical approach of BDE and BDFE determination was tested using 10 simple phenols, 5 flavonoids, and l-ascorbic acid derivatives. The agreement between our calculated gas phase results and the adopted experimental values were generally within 0.5 kcal mol?1, with a very few exceptions.

Discussion

Generally, steric interactions as well as intramolecular hydrogen bonding involving the dissociating OH group should be minimized in the GS. The DS are both electronically and vibrationally exited transition states. They have one unpaired electron on the carbon atom, which bears the homolytically dissociating OH group and are second order saddle points with a fixed <C–O–H bond angel of 180°.

Conclusion

It was concluded that ab initio UHF was well suited for the estimation of gas phase BDE and BDFE. The method presented has a good potential for application across a range of hydroxylic antioxidants. Currently, work is underway to extend its application in other class of antioxidants.  相似文献   

3.
In the present work, in order to investigate the electronic excited-state intermolecular hydrogen bonding between the chromophore coumarin 153 (C153) and the room-temperature ionic liquid N,N-dimethylethanolammonium formate (DAF), both the geometric structures and the infrared spectra of the hydrogen-bonded complex C153–DAF+ in the excited state were studied by a time-dependent density functional theory (TDDFT) method. We theoretically demonstrated that the intermolecular hydrogen bond C1?=?O1···H1–O3 in the hydrogen-bonded C153–DAF+ complex is significantly strengthened in the S1 state by monitoring the spectral shifts of the C=O group and O–H group involved in the hydrogen bond C1?=?O1···H1–O3. Moreover, the length of the hydrogen bond C1?=?O1···H1–O3 between the oxygen atom and hydrogen atom decreased from 1.693 Å to 1.633 Å upon photoexcitation. This was also confirmed by the increase in the hydrogen-bond binding energy from 69.92 kJ mol?1 in the ground state to 90.17 kJ mol?1 in the excited state. Thus, the excited-state hydrogen-bond strengthening of the coumarin chromophore in an ionic liquid has been demonstrated theoretically for the first time.  相似文献   

4.
We report geometries, stabilization energies, symmetry adapted perturbation theory (SAPT) and quantum theory of atoms in molecules (QTAIM) analyses of a series of carbene–BX3 complexes, where X = H, OH, NH2, CH3, CN, NC, F, Cl, and Br. The stabilization energies were calculated at HF, B3LYP, MP2, MP4 and CCSD(T)/aug-cc-pVDZ levels of theory using optimized geometries of all the complexes obtained from B3LYP/aug-cc-pVTZ. Quantitatively, all the complexes indicate the presence of B–Ccarbene interaction due to the short B–Ccarbene distances. Inspection of stabilization energies reveals that the interaction energies increase in the order NH2 > OH > CH3 > F > H > Cl > Br > NC > CN, which is the opposite trend shown in the binding distances. Considering the SAPT results, it is found that electrostatic effects account for about 50% of the overall attraction of the studied complexes. By comparison, the induction components of these interactions represent about 40% of the total attractive forces. Despite falling in a region of charge depletion with ∇2 ρ BCP >0, the B–Ccarbene bond critical points (BCPs) are characterized by a reasonably large value of the electron density (ρ BCP) and HBCP <0, indicating that the potential energy overcomes the kinetic energy density at BCP and the B–Ccarbene bond is a polar covalent bond.  相似文献   

5.
Geometrical structures and relative stabilities of (LiNH2)n (n = 1–5) clusters were studied using density functional theory (DFT) at the B3LYP/6-31G* and B3LYP/6-31++G* levels. The electronic structures, vibrational properties, N–H bond dissociation energies (BDE), thermodynamic properties, bond properties and ionization potentials were analyzed for the most stable isomers. The calculated results show that the Li–N and Li–Li bonds can be formed more easily than those of the Li–H or N–H bonds in the clusters, in which NH2 is bound to the framework of Li atomic clusters with fused rings. The average binding energies for each LiNH2 unit increase gradually from 142 kJ mol−1 up to about 180 kJ mol−1 with increasing n. Natural bond orbital (NBO) analysis suggests that the bonds between Li and NH2 are of strong ionicity. Three-center–two-electron Li–N–Li bonding exists in the (LiNH2)2 dimer. The N–H BDE values indicate that the change in N–H BDE values from the monomer a1 to the singlet-state clusters is small. The N–H bonds in singlet state clusters are stable, while the N–H bonds in triplet clusters dissociate easily. A study of their thermodynamic properties suggests that monomer a1 forms clusters (b1, c1, d2 and e1) easily at low temperature, and clusters with fewer numbers of rings tend to transfer to ones with more rings at low temperature. E g, E HOMO and E av decrease gradually, and become constant. Ring-like (LiNH2)3,4 clusters possess higher ionization energy (VIE) and E g, but lower values of E HOMO. Ring-like (LiNH2)3,4 clusters are more stable than other types. A comparison of structures and spectra between clusters and crystal showed that the NH2 moiety in clusters has a structure and spectral features similar to those of the crystal.  相似文献   

6.
7.
The Arrhenius kinetic parameters of dissociation reactions and reactions of CF3CH2I with radicals like H, O, and OH are determined using highly accurate first principles calculations. Thermophysical properties like molar heat capacity (Cp), thermal stability index, and the bond dissociation energies are also determined for the CF3CH2I molecule under the PBE/DNP formalism. Since, there are no theoretical study or experimental investigation reports available regarding the dissociation reactions of CF3CH2I and reactions of this molecule with the H and OH radical, a parallel comparative analysis is done with similar iodoalkanes to ascertain the precision of the results obtained. The atmospheric lifetime of 0.54 years is obtained for this molecule.  相似文献   

8.
Tocopheramines (TNH2) and tocotrienamines (T3NH2) are analogues of tocopherols (TOH) and tocotrienols in which phenolic OH is replaced by NH2. It was shown in previous studies that TNH2 and T3NH2 act as potent antioxidants. In this study we compared the one-electron oxidation of TNH2/T3NH2 by diphenyl picryl hydrazyl (DPPH) and galvinoxyl (GOX) radicals with the one of α-TOH as a reference compound using ESR spectroscopy, stopped flow spectrophotometry and density functional theory (DFT) calculations. ESR spectroscopy revealed the presence of tocopheramine radicals during electrochemical oxidation of α-TNH2. Kinetic measurements demonstrated that in apolar n-hexane TNH2/T3NH2 derivatives reacted two to three orders of magnitude slower than α-TOH with the model radicals. DFT calculations indicated that this correlates well with the higher bond dissociation energy (BDE) for N–H in TNH2 than for O–H in α-TOH in pure H-atom transfer (HAT). In the more polar medium ethanol TNH2/T3NH2 derivatives partially reacted faster than α-TOH depending on the reaction partner. DFT calculations suggest that this is due to reaction mechanisms alternative to HAT. According to thermochemistry data sequential proton loss and electron transfer (SPLET) is more favored for α-TOH in ethanol than for TNH2. Therefore, for TNH2 a contribution of the alternative mechanism of sequential electron transfer–proton transfer (SET–PT) could be a possible explanation. These data show that the antioxidant reactivity strongly depends on the structure, reaction partners and environment. According to these findings TNH2/T3NH2 should be superior as antioxidants over α-TOH in polar head group regions of membranes but not in the apolar core of lipid bilayers.  相似文献   

9.
The selectivity of phosphoryl P(O)R3, sulfoxide S(O)R2, and carbonyl C(O)R2 (R?=?NH2, CH3, OH, and F) derivatives with lanthanide cations (La3+, Eu3+, Lu3+) was studied by density functional theory calculations. Theoretical approaches were also used to investigate energy and the nature of metal–ligand interaction in the model complexes. Atoms in molecules and natural bond orbital (NBO) analyses were accomplished to understand the electronic structure of ligands, L, and the related complexes, L–Ln3+. NBO analysis demonstrated that the negative charge on phosphoryl, carbonyl, and sulfoxide oxygen (OP, OC, and OS) has maximum and minimum values when the connected –R groups are –NH2 and –F. The metal–ligand distance declines as, –F?>?–OH?>?–CH3?>?–NH2. Charge density at the bond critical point and on the lanthanide cation in the L–Ln3+ complexes varies in the order –F?<?–OH?<?–CH3?<?–NH2, due to greater ligand to metal charge transfer, which is well explained by energy decomposition analysis. It was also illustrated that E(2) values of Lp(N)?→?σ*(Y–N) vary in the order P=O ? S=O ? C=O and the related values of Lp(N)?→?σ*(Y=O) change as C=O ? S=O ? P=O in (NH2)nYO ligands (Y?=?P, C, and S). Trends in the L–Ln3+ CP–corrected bond energies are in good accordance with the optimized OY?Ln distances. It seems that, comparing the three types of ligands studied, NH2–substituted are the better coordination ligands.
Graphical Abstract Density functional theory (B3LYP) calculations were used to compare structural, electronic and energy aspects of lanthanide (La, Eu, Lu) complexes of phosphine derivatives with those of carbonyls and sulfoxides in which the R– groups connected to the P=O, C=O and S=O are –NH2, –CH3, –OH and –F.
  相似文献   

10.
《Inorganica chimica acta》1986,119(2):203-205
Reactions of cis-diaminediaqua palladium and platinum dinitrates and of trans-diaminediaqua platinum dinitrate give complexes of the type Pd(tmeda)(OH)(C4O4)Pd(tmeda)(C4O4H) (tmeda = tetramethylethylenediamine) (1), (en)M(C4O4)2M(en) (en = ethylenediamine (M = Pd, Pt) and trans-[Pt- (NH3)2C4O4]n, respectively. The structures of these compounds are discussed on the basis of their spectroscopic data.  相似文献   

11.
Vanadium-based catalysts are used in many technological processes, among which the removal of nitrogen oxides (NOx) from waste gases is one of the most important. The chemical reaction responsible for this selective catalytic reaction (SCR) is based on the reduction of NOx molecules to N2, and a possible reductant in this case is pre-adsorbed NH3. In this paper, NH3 adsorption on Brønsted OH acid centers on low-index surfaces of V2O5 (010, 100, 001) is studied using a theoretical DFT method with a gradient-corrected functional (RPBE) in the embedded cluster approximation model. The results of the calculations show that ammonia molecules are spontaneously stabilized on all low-index surfaces of the investigated catalyst, with adsorption energies ranging from ?0.34 to ?2 eV. Two different mechanisms of ammonia adsorption occur: the predominant mechanism involves the transfer of a proton from a surface OH group and the stabilization of ammonia as an NH4 + cation bonded to surface O atom(s), while an alternative mechanism involves the hydrogen bonding of NH3 to a surface OH moiety. The latter binding mode is present only in cases of stabilization over a doubly coordinated O(2) center at a (100) surface. The results of the calculations indicate that a nondirectional local electrostatic interaction with ammonia approaching a surface predetermines the mode of stabilization, whereas hydrogen-bonding interactions are the main force stabilizing the adsorbed ammonia. Utilizing the geometric features of the hydrogen bonds, the overall strength of these interactions was quantified and qualitatively correlated (R?=?0.93) with the magnitude of the stabilization effect (i.e., the adsorption energy).
Figure
Two different modes (NH3/NH4 +) of ammonia adsorption on the (001)V2O5 net plane.  相似文献   

12.
Abstract

While it is well established that classical hydrogen bonds play an important role in enzyme structure, function and dynamics, the role of weaker, but ‘activated’ C-H donor hydrogen bonds is poorly understood. The most important such case involves histidine which often plays a direct role in enzyme catalysis and possesses the most acidic C-H donor group of the standard amino acids. In the present study, we obtained optimized geometries and hydrogen bond interaction energies for C-H…O hydrogen bonded complexes between methane, ethylene, benzene, acetylene, and imidazole with water at the MP2-FC/6-31++G(2d,2p) and MP2-FC/aug-cc-pVDZ//MP2-FC/6-31++G(2d,2p) levels of theory. A strong linear relationship is obtained between the stability of the various hydrogen bonded complexes and both separation distances for H…0 and C—O. In general, these calculations indicate that C-H…0 interactions can be classified as hydrogen bonding interactions, albeit significantly weaker than the classical hydrogen bonds, but significantly stronger than just van der Waals interactions. For instance, while the electronic energy of stabilization at the MP2-FC/aug-cc-pVDZ//MP2-FC/6-31++G(2d,2p) level of theory of a water C-H…O water hydrogen bond is 4.36 kcal/mol more stable than the methane C-H…O water interaction, the water-water hydrogen bond is only 2.06 kcal/mol more stable than the imidazole Ce?H…O water hydrogen bond. Neglecting this latter hydrogen bonding interaction is obviously unacceptable. We next compare the potential energy surfaces for the imidazole Ce?H…O water and imidazole Nd?H…O hydrogen bonded complexes computed at the MP2/6-31++G(2d,2p) level of theory with the potential energy surface computed using the AMBER molecular mechanics program and forcefields. While the Weiner et al and Cornell et al AMBER forcefields reasonably account for the imidazole N-H…O water interaction, these forcefields do not adequately account for the imidazole Ce?H…O water hydrogen bond. A forcefield modification is offered that results in excellent agreement between the ab initio and molecular mechanics geometry and energy for this C-H…O hydrogen bonded complex.  相似文献   

13.
A theoretical study of the chemisorption and dissociation pathways of water on the Al13 cluster was performed using the hybrid density functional B3LYP method with the 6-311+G(d, p) basis set. The activation energies, reaction enthalpies, and Gibbs free energy of activation for the reaction were determined. Calculations revealed that the H2O molecule is easily adsorbed onto the Al13 surface, forming adlayers. The dissociation of the first H2O molecule from the bimolecular H2O structure via the Grotthuss mechanism is the most kinetically favorable among the five potential pathways for O–H bond breaking. The elimination of H2 in the reaction of an H2O molecule with a hydrogen atom on the Al cluster via the Eley–Rideal mechanism has a lower activation barrier than the elimination of H2 in the reaction of two adsorbed H atoms or the reaction of OH and H. Following the adsorption and dissociation of H2O, the structure of Al13 is distorted to varying degrees.
Figure
Potential energy surface along the reaction coordinate for steps 5–9, calculated at the B3LYP/6-311+G(d,p) level  相似文献   

14.
How do lithium atoms affect the first hyperpolarizability (β0) of boron–nitrogen (BN) edge-doped graphene. In this work, using pentacene as graphene model, Lin@BN-1 edge-doped pentacene and Lin@BN-2 edge-doped pentacene (n?=?1, 5) were designed to study this problem. First, two models (BN-1 edge-doped pentacene, and BN-2 edge-doped pentacene ) were formed by doping the BN into the pentacene with different order, and then Li@BN-1 edge-doped pentacene and Li@ BN-2 edge-doped pentacene were obtained by substituting the H atom in BN edge-doped pentacene with a Li atom. The results show that the first hyperpolarizabilities of BN-1 edge-doped pentacene and Li@BN-1 edge-doped pentacene were 4059 a.u. and 6249 a.u., respectively; the first hyperpolarizabilities of BN-2 edge-doped pentacene and Li@BN-2 edge-doped pentacene were 2491 a.u. and 4265 a.u., respectively. The results indicate that the effect of Li substitution is to greatly increase the β0 value. To further enhance the first hyperpolarizability, Li5@ BN-1 edge-doped pentacene and Li5@BN-2 edge-doped pentacene were designed, and were found to exhibit considerably larger first hyperpolarizabilities (β0) (12,112 a.u. and 7921a.u., respectively). This work may inspire further study of the nonlinear properties of BN edge-doped graphene.  相似文献   

15.
A quantum chemistry study was carried out to investigate the strength and nature of halogen bond interactions in HXeH···XCCY complexes, where X = Cl, Br and Y = H, F, Cl, Br, CN, NC, C2H, CH3, OH, SH, NH2. Examination of the electrostatic potentials V(r) of the XCCY molecules reveals that the addition of substituents has a significant effect upon the most positive electrostatic potential on the surface of the interacting halogen atom. We found that the magnitude of atomic charges and multipole moments depends upon the halogen atom X and is rather sensitive to the electron-withdrawing/donating power of the remainder of the molecule. An excellent correlation was found between the most positive electrostatic potentials on the halogen atom and the interaction energies. For either HXeH···ClCCY or HXeH···BrCCY complexes, an approximate linear correlation between the interaction energies and halogens multipole moments are established, indicating that the electrostatic and polarization interactions are responsible for the stability of the complexes. According to energy decomposition analysis, it is revealed that the electrostatic interactions are the major source of the attraction in the HXeH···XCCY complexes. Furthermore, the changes in the electrostatic term are mainly responsible for the dependence of interaction energy on the halogen atom.
Graphical abstract
Electrostatic potential mapped on the surface of molecular electron density at the 0.001 electrons Bohr ?3 of HXeH. The color ranges in kcal mol?1 red >8.5, yellow 1.5 to 8.5, green ?5.5 to 1.5, blue <?5.5. Black and blue circles are referred to surface maxima and minima, respectively.  相似文献   

16.
The hydroxylamine mechanism of cyclohexanone ammoximation on defective titanium active site of titanium silicalite-1 (TS-1) was simulated using two-layer ONIOM (M062X/6-31G**:PM6) method. A new energy favorable reaction route was found, which contained two parts: (1) the catalytic oxidation of adsorbed NH3 to form hydroxylamine using the Ti-OOH as an active oxidant formed by reacting H2O2 with the defective Ti active site; (2) the subsequent noncatalytic oximation of desorbed hydroxylamine and cyclohexanone out of TS-1 pores to form cyclohexanone oxime. In the catalytic formation of hydroxylamine on the Ti active site of TS-1, the proposed mechanism of two-step single-proton transfer aided by a lattice oxygen atom bonded to Ti atom need a lower reaction energy than the mechanism proposed before. In the subsequent noncatalytic oximation of hydroxylamine and cyclohexanone, which contained two elementary reaction steps in total, the mechanisms of one-step double-proton transfer in the first elementary reaction step and the subsequent one-step three-proton transfer for the second elementary reaction step were proposed, in which the solvent water molecules played a very important role in assisting and stabilizing the proton transfer processes.  相似文献   

17.
Proton hopping is the process where a H‐atom on a hydronium ion forms a H‐bond with the O‐atom of a neighboring H2O molecule. There is then an exchange of bonding forces when that covalent bond of the H‐atom in the hydronium ion changes to a H‐bond, and the previous H‐bond changes to a covalent bond with the neighboring O‐atom. The neighboring molecule now becomes a hydronium (H3O+) ion. This process repeats itself very rapidly among neighboring hydronium and H2O molecules. There is a flow of protonic character through bulk H2O, referred to as proton hopping. This process carries information through living systems where H2O is present. A cellular automata model of proton hopping down a channel has been created and studied. Variations in the rate of proton entry into the channel and the effects of the polar character of the channel walls was studied using the model. The behavior of the models corresponds to experimental results.  相似文献   

18.
Theoretical investigations are carried out on reaction mechanism of the reactions of CF3CH2NH2 (TFEA) with the OH radical by means of ab initio and DFT methods. The electronic structure information on the potential energy surface for each reaction is obtained at MPWB1K/6-31+G(d,p) level and energetic information is further refined by calculating the energy of the species with a Gaussian-2 method, G2(MP2). The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. Our calculation indicates that the H abstraction from –NH2 group is the dominant reaction channel because of lower energy barrier. The rate constants of the reaction calculated using canonical transition state theory (CTST) utilizing the ab initio data. The agreement between the theoretical and experimental rate constants is good at the measured temperature. From the comparison with CH3CH2NH2, it is shown that the fluorine substution decreases the reactivity of the C-H bond.  相似文献   

19.
Arthrobacter sp. strain PBA metabolized phenylboronic acid to phenol. The oxygen atom in phenol was shown to be derived from the atmosphere using 18O2. 1-Naphthalene-, 2-naphthalene-, 3-cyanophenyl-, 2,5-fluorophenyl-, and 3-thiophene-boronic acids were also transformed to monooxygenated products. The oxygen atom in the product was bonded to the ring carbon atom originally bearing the boronic acid substituent with all the substrates tested.  相似文献   

20.
The platinum(II) complexes of the formula [Pt(DCHEDA)X2], where DCHEDA is N,N′-dicyclohexylethylenediamine and X is CL, Br, I, 0.5C2O42− (oxalate), 0.5C3H2O42− (malonate), 0.5C9H4O62− (4-carboxyphthalate), 0.5S2O32− or 0.5SO42−, have been synthesized and characterized by UVVis, IR, and 1H NMR spectral techniques. All the above complexes are non-electrolytes in DMF/H2O, except the sulphate complex which becomes a 1:1 electrolyte after incubation for 24 h at 28 °C. The halide complexes were also studied by X-ray photoelectron spectroscopy and these data suggest that there is π-bonding from platinum to halide in these complexes. The oxalate, malonate and sulphate bind in their complexes as bidentate ligands to platinum through two oxygen atoms whereas the thiosulphate in its complex binds as a bidentate ligand to platinum through one oxygen atom and one sulphur atom.  相似文献   

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