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1.
Bond dissociation energies for removal of nitrogen dioxide groups in 10 aliphatic nitro compounds, including nitromethane, nitroethylene, nitroethane, dinitromethane, 1-nitropropane, 2-nitropropane, 1-nitrobutane, 2-methyl-2-nitropropane, nitropentane, and nitrohexane, are calculated using the highly accurate complete basis set (CBS-Q) and the three hybrid density functional theory (DFT) methods B3LYP, B3PW91 and B3P86 with 6-31G^** basis set. By comparing the computed bond dissociation energies and experimental results, we find that the B3LYP/6-31G^** and B3PW91/6-31G^** methods are incapable of predicting the satisfactory bond dissociation energy (BDE). However, B3P86/6-31G^** and CBS-Q computations are capable of giving the calculated BDEs, which are in extraordinary agreement with the experimental data. Nevertheless, since CBS-Q computational demands increase rapidly with the number of containing atoms in molecules, larger molecules soon become prohibitively expensive. Therefore, we suggest to take the B3P86/6-31G^** method as a reliable method of computing the BDEs for removal of the NO2 groups in the aliphatic nitro compounds.  相似文献   

2.
The density functional theory (DFT) is the most popular method for evaluating bond dis-sociation enthalpies (BDEs) of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com-posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark values for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems (atoms number ≤20); the double-hybrid DFT methods are advised for large aromatic molecules in medium size (20 ≤atoms number ≤50), and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are advised to apply for large systems (atoms number ≥50), and the M06-2X and B3P86 methods are also favorable. Moreover, the di erences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.  相似文献   

3.
By using the density functional theory (B3LYP) and four highly accurate complete basis set (CBS-Q, CBS-QB3, CBS-Lq, and CBS-4M)ab initio methods, the X(C, N, O)-NO2 bond dissociation energies (BDEs) for CH3NO2, C2H3NO2, C2H5NO2, HONO2, CH3ONO2, C2H5ONO2, NH2NO2 (CH3)2NNO2 are computed. By comparing the computed BDEs and experimental results, it is found that the B3LYP method is unable to predict satisfactorily the results of bond dissociation energy (BDE); however, all four CBS models are generally able to give reliable predication of the X(C, N, O)-NO2 BDEs for these nitro compounds. Moreover, the CBS-4M calculation is the least computationally demanding among the four CBS methods considered, Therefore, we recommend CBS-4M method as a reliable method of computing the BDEs for this nitro compound system.  相似文献   

4.
The compound (4-chlorophenyl)-N-(4-methylphenyl) nitrone (4CPNMPN) has been selected as one of the new nitrone derivative for our study. The molecular structure of the compound was investigated based on frontier orbital analysis and natural bond orbital (NBO) theory. The present work also focuses on the inhibition efficiency of the compound. It is an attempt to find the correlation between the molecular structure of the compound and possible behaviour like corrosion inhibitors. The NBO analysis and the values of electric dipole moment (μ) of the investigated molecule were computed using DFT calculations. The molecule orbital contributions were studied by using the total (TDOS) density of states. The strong evidences that the compound can be used as an efficient nonlinear optical (NLO) of 4CPNMPN were demonstrated by considerable polarizability and hyperpolarizability values obtained at DFT levels.  相似文献   

5.
Equilibrium parameters of ozone, such as equilibrium geometry structure parameters, force constants and dissociation energy are presented by CBS-Q ab initio calculations. The calculated equilibrium geometry structure parameters and energy are in agreement with the corresponding experimental values. The potential energy function of ozone with a C2v symmetry in the ground state is described by the simplified Sorbie-Murrell many-body expansion potential function according to the ozone molecule symmetry. The contour of bond stretching vibration potential of an O3 in the ground state, with a bond angle (θ) fixed, and the contour of O3 potential for O rotating around O1-O (R1), with O1-O bond length taken as the one at equilibrium, are plotted. Moreover, the potentials are analysed.  相似文献   

6.
Density functional theory(DFT) is applied to investigate the stability and mechanical properties of NbxCy compounds.The structures of NbxCy compounds are optimized, and the results are in good agreement with previous work. The calculated results of the cohesive energy and the formation enthalpy of NbxCy show that they are thermodynamically stable structures, except for Pmc21-Nb2 C. The mechanical properties such as the bulk modulus, Young’s modulus, the shear modulus, and Poisson’s ratio are obtained by Voigt–Reuss–Hill approximation. The results show that the Young’s modulus and shear modulus of NbC are larger than other NbxCy compounds. The mechanical anisotropy is characterized by calculating several different anisotropic indexes and factors, such as universal anisotropic index(AU), shear anisotropic factors(A1, A2,A3), and percent anisotropy(ABand AG). The surface constructions of bulk and Young’s moduli are illustrated to indicate the mechanical anisotropy. The hardness of NbxCy compounds is also discussed in this paper. The estimated hardness for all NbxCy compounds is less than 20 GPa.  相似文献   

7.
曾晖  赵俊 《中国物理 B》2014,(6):150-157
Density functional theory calculations at the B3LYP/6-311G** level are performed to study the geometric and elec- tronic structures of a series of nitroaliphatic compounds. The heats of formation (HOF) are predicted through the designed isodesmic reactions. Thermal stabilities are evaluated via the homolytic bond dissociation energies (BDEs). Further, the correlation is developed between impact sensitivity h50% and the ratio (BDE/E) of the weakest BDE to the total energy E containing zero point energy correction. In addition, the relative stability of the title compounds is evaluated based on the analysis of calculated Mulliken population and the energy gaps between the frontier orbitals. The calculated BDEs, HOFs, and energy gaps consistently indicate that compound 1,1,1,6,6,6-hexanitro-3-hexyne is the most unstable and the compound 3,3,4,4,-tetranitro-hexane is the most stable. These results provide basic information for the molecular design of novel high energetic density materials.  相似文献   

8.
It is of great significance to study the relationship between the excited state intramolecular proton transfer(ESIPT)properties and antioxidant activities of compounds in the field of life sciences. In this work, two novel compounds 5 HF–OMe and 5 HF–NH2 are designed through introducing a methoxy-and amino-group into the structure of 5-hydroxyflavone(5 HF) respectively. The relationship between the ESIPT reaction and antioxidant activities of the three compounds is studied via the density functional theory(DFT) and time-dependent DFT(TD-DFT) methods. The calculated potential energy curves suggest that the rate of ESIPT reaction will gradually slow down from 5 HF to 5 HF–OMe and 5 HF–NH2.In addition, the antioxidant activities of the three compounds gradually enhance from 5 HF to 5 HF–OMe and 5 HF–NH2,which can be seen from the calculated energy gaps and ionization potential values. Interestingly, the above results imply that the rate of ESIPT reaction has a negative relationship with the antioxidant activities of the compounds, i.e., the slower rate of ESIPT reaction will reflect the higher antioxidant activity of the compound, which will provide valuable reference for detecting the antioxidant activity of compound via the photophysical method.  相似文献   

9.
Inelastic mean free paths (MFPs) of 0.05-10 MeV protons in a group of 10 organic compounds are systematically calculated. The calculations are based on the method newly derived from the Ashley optical-data model and from the higher-order correction terms in stopping power calculations. Especially, in this method the new and empirical Bloch correction for the inelastic MFP is given. An evaluation for the optical energy loss function is incorporated into the present calculations because of the lack of available experimental optical data for the considered organic compounds expect for kapton. The proton inelastic MFPs for these 10 organic compounds in the energy range from 0.05 to 10 MeV are presented here for the first time, and the combination of these inelastic MFP data and our previous data of stopping power calculation for these bioorganic compounds may form a useful database for Monte Carlo track-structure studies of various radiation effects on these materials.  相似文献   

10.
The ground state hydrogen conformations and vibrational analysis of 3-deazauracil (3DAU) and 6-azauracil (6AU) tautomers (4-enol and 2,4-diol forms) have been calculated using ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods with 6-311++G(d,p) basis set level. The calculations have shown that the most probably preferential tautomer of 3DAU and 6AU are the 4-enol form, which gives best fit to the corresponding experimental data. The ground state conformer of the 2,4-diol form has two O-H bonds which are oriented externally and internally (to the N-H bond). The vibrational analyses of the ground state conformer of each tautomeric form of 3DAU and 6AU were done and their optimized geometry parameters (bond lengths and bond angles) were given. Furthermore, from the correlations values it was concluded that the B3LYP method is superior to the HF method for both the vibrational frequencies and the geometric parameters.  相似文献   

11.
利用密度泛函(DFT)三种交换/相关函数(B3LYP, B3PW91,B3P86)结合6-31G**和6-311G**基组,计算了13个取代氯苯化合物的键离解能. 结果表明B3P86/6-311G**方法是计算取代氯苯化合物键离解能的可信方法,研究发现C-Cl键的键离解能与所使用的基组和计算方法密切相关,取代基对C-Cl键的键离解能的影响不明显. 研究了目标化合物的前线轨道能级差,并对取代氯苯化合物的热稳定性做了评估.  相似文献   

12.
三硝基甲烷键离解能和生成焓的理论计算   总被引:5,自引:0,他引:5  
采用密度泛函(DFT)四种交换/相关函数(B3LYP、B3P86、B3PW91和PBE0)结合不同的基函数,求得了三硝基甲烷C-NO2键的离解能(BDE),并且通过合理选择参考物硝基甲烷,设计等键等电子对反应,计算了气相三硝基甲烷分子的生成焓(HOF).与实验数据进行比较,PBE0/6-31g*计算出的BDE值最好,误差为-2.1 kcal mol-1;PBE0密度泛函结合带极化函数的6-31g基组得到的HOF值与实验值吻合的最好(误差在0.1 kcal mol-1以内).  相似文献   

13.
The molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) 1H and 13C chemical shift values of ABZ-TNB [ABZ-TNB: 2-aminobenzimidazole-trinitrobenzene] and ABZ-PA [ABZ-PA: 2-aminobenzimidazole-picric acid] in the ground state were calculated by using density functionals (B3LYP and PBE1PBE) and Hartree-Fock (HF) methods with the 6–31 ++ G(d,p) basis set. Furthermore, the electronic spectrum of title complexes was calculated with the time dependent DFT levels (TD-PBE1PBE and TD-B3LYP) and HF (TD-HF) method starting from the ground state geometry optimized in the gas phase. A detailed assignment of vibrational spectra was made on the basis of the calculated potential energy distribution (PED). Total static dipole moment (μ), the mean polarizability (〈α〉), the anisotropy of the polarizability (Δα), the mean first-order hyperpolarizability (〈β〉), highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies, chemical hardness (η) and electronegativity (χ) of ABZ-TNB and ABZ-PA complexes were also investigated with quantum chemical calculations. Additionally, data obtained from quantum chemical calculations were compared with the experimental ones.  相似文献   

14.
Five density functional theory (DFT) methods including B3LYP, B3PW91, MPW1K, MPWB, TPSS1KCIS have been evaluated by comparing with the experimental O? H bond dissociation enthalpies (BDEs) of substituted phenols. B3PW91 is found to be the best method, for which the calculation error was 3.62 kJ/mol. Subsequently, the BDEs (O? H) of hydroxyl groups on five‐ and six‐membered heteroatomic aromatic rings have been calculated using the (RO)B3PW91/6‐311++G(2df,2p)//(U)B3LYP/6‐311g(d,p) procedure. In addition, the ionization energy (IE) and proton affinity [PA(O?)] of these compounds have also been examined. On the basis of our theoretical study, a series of imidazolols, thiazolols, and oxazolols were studied to assess their antioxidant activities. It was found that 5‐oxazolol could be a promising novel antioxidant precursor. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

15.
用密度泛函(B3P86/6-311g*)方法研究了Ni2分子结构和势能函数.结果表明基态Ni2为5Πg,平衡间距为Re=0.223 196 nm,离解能为1.851 16 eV.定义了分子轨道密度(DMO, density of molecular orbital)并研究了镍双原子分子的s, p, d, f的DMO对成键的贡献,为进一步研究金属的态密度提供了有益的参考价值.  相似文献   

16.
凌智钢  唐延林  李涛  李玉鹏  魏晓楠 《物理学报》2014,63(2):23102-023102
对O原子采用6-311++G*基组,Zr原子采用aug-cc-pVTZ-PP基组,利用密度泛函(B3P86)方法优化得到了ZrO2分子的稳定构型,并研究了不同外电场(0—0.025 a.u.)作用下ZrO2基态分子键长、能量、电荷分布、偶极矩和能级的变化规律.在优化构型的基础上,利用含时密度泛函(TD-B3P86)方法研究了ZrO2分子在外电场作用下前6个激发态的激发能、跃迁波长和振子强度的激发特性.研究结果表明:随着电场强度的增大,Zr—2O的键长增大,而Zr—3O的键长均匀减少,总能量降低,偶极矩增大;最高占据轨道能量基本保持不变,最低未占据轨道和能隙均减小.电场的增大使得激发能减小,各个激发态跃迁波长均发生不同程度的红移现象,因而,利用外电场可以控制ZrO2的发光光谱范围在可见-红外区域扩展.  相似文献   

17.
The magnetic interaction in an orbitally degenerate transition metal dimer complex is investigated using a typical example of a d(1)-d(1) dimer complex, the Ti2Cl9(3-) cluster. The local orbital functions are defined by linear combinations of the molecular orbital functions which are calculated by density functional theory (DFT). In the DFT calculation, the Perdew-Burke-Ernzerhof (PBE) functional and hybrid PBE0 functional are utilized. The matrix elements of the effective Hamiltonian of the d-electrons are evaluated by the DFT calculation except for one parameter which is determined by comparing the zero-temperature magnetic susceptibility in the direction along the c axis χ(∥) with the experimental result. By the calculation with the PBE0 functional, the zero-temperature magnetic susceptibility in the perpendicular direction χ(⊥) and the temperature dependence of the susceptibilities in both directions agree with the experiment. On the other hand, by the calculation with the PBE functional, χ(⊥) is smaller than the experimental values because the on-site potential is underestimated.  相似文献   

18.
外场下SnS分子结构及其特性   总被引:1,自引:0,他引:1       下载免费PDF全文
黄多辉  王藩侯  万明杰  蒋刚 《物理学报》2013,62(1):13104-013104
对S原子采用6-311++G**基组,Sn原子采用SDB-cc-pVTZ基组,利用密度泛函(B3P86)方法对SnS分子进行了基态结构优化,并研究了外场作用下SnS基态分子键长、能量、能级分布、电荷布居分布、谐振频率和红外谱强度的影响规律.然后利用含时密度泛函(TD-B3P86)方法研究了SnS分子在外场下的激发特性.结果表明,在所加的电场范围内(-0.04 a.u.-0.04 a.u.),随着正向电场的增大,分子键长和红外谱强度均是先减小后增大;总能E,SnS基态分子的最高已占据轨道能量EH和谐振频率均是先增大后减小;分子的最低未占空轨道能量EL和能隙Eg均随正向电场的增大而减小.随着正向电场的增大,SnS分子由基态至前9个单重激发态跃迁的波长增大,激发能则减小.  相似文献   

19.
用Gaussian03W程序在B3LYP/631G和HF/631G水平上对二苯二硫(DPDS)和二苄二硫(DBDS)的分子几何构型、电子结构、分子轨道指数及与铁原子簇的相互作用等进行了理论计算.用前线分子轨道理论分析了反应的活性原子和活性键,讨论了DPDS和DBDS与铁原子的作用方式,用前线电子密度,超离域性指数,原子净电荷及化合物与铁原子簇的化学吸附作用能等参数作为判据分析了DPDS和DBDS与铁原子间键合的强弱,反应性的大小.计算结果表明DPDS和DBDS与铁接触时,趋向于S-S键与C-S键断裂,在较为缓和的摩擦条件下,DPDS的抗磨作用优于DBDS,在较为苛刻的摩擦条件下,DBDS的极压作用优于DPDS,与摩擦学试验结果一致.  相似文献   

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