电场中R-NO_2…HF(R=-CH_3、-NH_2、-OCH_3)氢键复合物结构及性能的理论研究

采用密度泛函B3LYP方法,在6-311++G(2d,p)水平上对外电场中的R-NO_2(R=-CH_3、-NH2、-OCH3)及其HF氢键体系(R-NO2…HF)进行了结构优化,然后在6-311++G(2d,p)和aug-cc-p VTZ基组水平上分别用B3LYP和MP2(full)方法进行了能量计算,并对单体R-NO_2在CCSD(T)方法下进行了更为详细的考量,最后借助分子中的原子(AIM)理论以及分子静电势揭示了结构和能量变化的本质.结果表明,在一定方向和大小的外电场作用下,单体分子的相对总能量降低,引发键键长变短,偶极矩增大,引发键离解能变大;氢键复合物比其单体引发键键长更短,引发键键能也更大.     

UX(X=H,F,Cl,Br)的分子结构与稳定性

用密度泛函B3LYP方法对UX(X=H,F,Cl,Br)分子体系进行了理论研究,结果表明, 这些分子的基态电子状态分别是X4Ⅱ、X6∑、X2∑、X6∑,且都能稳定存在,其中UBr最 稳定,UH稳定性最差;势能函数为Murrell-Sorbie势函数,并得到了相应的几何性质、力 学性质和光谱数据。     

CX2+CH2O (X=F, Cl, Br)环加成反应的密度泛函理论计算

用密度泛函理论,在B3LYP/6-311 G(d)水平上研究了CX2 CH2O(X=F,Cl,Br)环加成反应一条三过渡态三中间体路径的反应机理,全参数优化了反应势能面各驻点的几何构型,用内禀反应坐标(IRC)和频率分析方法,对过渡态进行了验证.用高级电子相关校正的耦合簇[CCSD(T)/6-311 G(d)]方法对优化构型进行了单点能计算.采用经Wigner校正的Eyring过渡态理论和热力学方法,研究了该反应通道的热力学及动力学性质.从热力学和动力角度综合分析,该途径CF2与GH2O的环加成反应难以发生,而CCl2及CBr2与CH2O反应的适宜温度范围均为400～1000K,如此,反应既具有较大的自发趋势和平衡常数,又具有较快的反应速率.     

HX(X=F,Cl,Br)酸性强度的理论计算

本文用Gibbs自由能ΔGacid定义了HX(g)的酸性强度.研究表明,用MP2、QCISD和B3LYP三种量化方法计算所得的HX酸性强度与文献值对比,其最大的相对误差仅为2.45%.其中,B3LYP方法的计算结果与文献值最为接近,其误差在0.37-1.09%范围内.HF气态分子有明显的氢键作用,其二聚体分子酸性强度ΔGacid与单体分子的ΔGacid值相比降低了约-5～-11%,此时氟化氢气体的酸性强度已不能单从HF单体分子的ΔGacid值来衡量,而应考虑HF分子的氢键作用.     

M-Uracil复合物(M=Ca2+和Mg2＋)特征振动的密度泛函理论分析

采用密度函数理论的B3LYP交换关联能泛函在6-311 G(2df,2p)基组水平上,对Ca2 、Mg2 与尿嘧啶(简称U)三种各互变异构体(简称U1、U2和U3)形成的复合物进行了优化计算,获得稳定复合物的构形,并对这些稳定复合物进行振动频率计算.分析计算结果发现由于离子的参与,单体分子振动的力常数和折合质量均会发生变化,导致红外振动谱线发生不同程度移动;进一步分析发现C-H和O-H键的氢原子作弯曲振动和伸缩振动的谱线移动不确定,直接与离子作用的氧原子参与的振动谱线会发生红移,不直接与离子作用的氧原子参与的振动谱线会发生蓝移.     

CnH2n(n=2,3,4)与BX3(X=H,F,Cl)作用的DFT研究

用量子化学的密度泛函理论方法对BX3(X=H,F,Cl)与烯烃CnH2n(n=2,3,4)形成的复合物进行了研究,结果表明,复合物的构型皆为BX3位于烯烃π键的上方,并且偏向氢原子数较多的碳原子一侧.C-C双键中的π电子通过向BH3中B的空p轨道转移电子而形成复合物,但BF3和BCl3与烯烃分子只是通过微弱的分子间作用力结合,复合物的形成使分子的振动光谱随作用的强弱而出现一定的红移现象.     

二聚物X2 和 XK (X= Mn, Fe, Co, Ni, Cu)吸附NO的密度泛函理论研究

为有效降低NO对环境以及人体造成的危害,着重从催化剂入手,研究过渡金属Mn₂, Fe₂, Co₂, Ni₂, Cu₂及K掺杂的MnK, FeK, CoK, NiK, CuK的二聚物对NO的吸附性能.采用密度泛函理论的B3LYP, B3PW91, B3P86, B1B95以及PBE1PBE方法结合LANL2DZ, SDD, CEP-121G基组,采用B3LYP, B3PW91, B3P86以及PBE1PBE方法结合6-31++G(3df, 3pd), 6-311++G(3df, 3pd), 6-31G(d, p), LANL2DZ, SDD基组分别系统研究了X₂和XK (X=Mn, Fe, Co, Ni, Cu)团簇和NO的几何结构,计算出其键长,频率,离解能,再与对应的实验值进行对比.进一步采用PBE1PBE方法结合LANL2DZ和6-31G(d, p)基组研究了X₂NO和KXNO团簇的几何结构,计算出各原子间键长和吸附能.结果表明,...     

CX2(X=F, Cl, Br)与CH3CHO中C－C键插入和环加成的理论模拟

采用密度泛函[DFT]和自然键轨道理论[NBO]及高级电子耦合簇[CCSD(T)]和电子密度拓扑分析[AIM]方法, 研究了单重态二卤卡宾CX2(X=F, Cl, Br)与乙醛CH3CHO 中C—C键的插入反应及其环加成的反应机理. 在B3LYP/6-31G(d)水平上优化了各驻点构型, 用频率分析和内禀反应坐标法(IRC)对过渡态进行了验证, 计算了各物种的CCSD(T)/6-31G(d, p)单点能量. 用经Wigner校正的Eyring过渡态理论分别计算了1大气压下主反应通道的热力学与动力学性质, 并对反应通道中构型进行了自然键轨道及电子密度拓扑分析. 结果表明, CF2与CH3CHO反应的主产物是P2F[CH3CF2CHO: 插入CH3CHO中C-C键, 反应I(2)], 而CCl2及CBr2与CH3CHO反应的主产物是P1Cl[Cl2COCHCH3: 成环反应II(1)]及P1Br[Br2COCHCH3: 成环反应III(1)], 1大气压下, 反应I(2)和II(1)及III(1)进行的适宜温度范围分别为400~1300K和400~1000K.     

氢键和分子-离子相互作用对奥克托今(HMX)引发键影响的理论研究

为了寻找能够降低炸药感度的方法,借助B3LYP和MP2(full)理论,在B3LYP/6-311++G(2df,2p)、B3LYP/aug-cc-p VTZ和MP2(full)/6-311++G(2df,2p)三种水平下,分别研究了与HMX形成的12种复合物(六种氢键复合物和六种分子-离子复合物),并对引发键N-NO2键长和强度的变化及硝基电荷的变化等进行了详细的考量,最后借助分子中原子(AIM)理论揭示了结构和能量变化的本质.结果表明,在形成复合物后,引发键键长变短,离解能增大,硝基电荷增多,引发键增强,感度降低,同时引发键离解能的变化(ΔBDEs)与这两种相互作用能呈良好的线性关系(R2=0.9984).     

黑索金的电子结构和热解机理的从头算研究

利用从头算梯度修正密度泛函理论,我们在B3LYP/6-31G(d,p)水平上,计算了高能炸药黑索金(RDX)及其热解中间产物C3H6N5O4和NO2等的电子结构、能量、键级和一些热力学性质,并在此基础上,计算了键离解能和反应速率常数.此外,我们还分别从键级和键离解能角度,讨论了RDX的热解机理,所得结果与实验一致.     

Relativistic density functional investigation of UX6（X=F,Cl,Br and I）

The molecular structures and the vibrational frequencies of uranium hexahalides UX 6(X=F,Cl,Br and I) molecules are investigated by using local density approximation(LDA) and generalised gradient approximation(GGA) functions(BP,BLYP and RPBE) in combination with two different relativistic methods(scalar and scalar+spin-orbit relativistic effects).The calculated results show that the differences are trivial between scalar and scalar+spin-orbit relativistic methods.The vibrational frequencies are also compared with existing experimental values,and overall,the RPBE approach gives the smallest error.The bond dissociation energies(BDEs) of UX 6 are computed by using the RPBE function,thereby obtaining exact vibrational frequencies.In addition,the calculated magnitudes of the spin-orbit effect on the BDE of UX 6(X=F,Cl,Br,and I) are found to be approximately-0.3198,-0.3218,-0.3609 and-0.4415 eV,respectively.     

Luminescence of MeFX : Eu2+ (Me = Sr,Ba; X = Cl,Br)

Compounds of the type MeFX : Eu²⁺ with Me = Sr, Ba and X = C1, Br are efficient phosphors. Emission consists of both a 5d-4f band as well as 4f-4f lines, their relative intensities being strongly dependent on host lattice and temperature.     

Spectroscopy and dissociation of sulfuryl halides SO2X2 (X=F,Cl)

The spectroscopy and dissociation of the sulfuryl halides SO₂F₂ and SO₂Cl₂ have been studied in detail using ab initio methods. The possibility of various dissociation channels has been explored taking into account that the fragmented atoms and molecules can stay in their ground state only. An interesting pattern was observed in their dissociation energy spectra for the dissociation channels. The singlet potential energy surfaces for the exit channels of these molecules have been analysed. The release of halogen molecules after dissociation is discussed from an industrial point of view. Finally, the enthalpy of formation of these molecules was computed using the ab initio results. Our results agree very well with the experimental values available.     

Photostimulated luminescence in BaX 2 :Eu 2+ (X=Br,Cl) X-ray storage phosphors

The photostimulated luminescence (PSL) effect in BaX 2 :Eu 2+ (X=Br, Cl) is comparable to that observed in BaFBr:Eu 2+ which is used in commercial X-ray storage phosphor screens. After X-irradiation the PSL stimulation spectra of BaX 2 :Eu 2+ (X=Br, Cl) single crystals are identical to the F centre absorption spectra, i.e. the F centres are the PSL-active electron trap centres. The nature of the hole centres is still unknown. The PSL response time of about 0.70 v s is within experimental error of 0.02 v s identical to the Eu 2+ radiative lifetime, whereas in BaCl 2 :Eu 2+ the PSL response time is 0.60 v s, and thus longer than the Eu 2+ radiative lifetime of 0.47 v s.     

DFT study of the water/MgO(1 0 0) interface in acidic and basic media

Periodic-DFT has been used to study the acid-base properties of MgO(1 0 0) layers interconnected with an ice filling. The insertion of HCl by substitution of one water molecule shows that all the protons are adsorbed on the surface oxygen atoms forming hydroxyl groups; the Cl⁻ ions are weakly bound to surface cations, generating a monolayer with the adsorbed water molecules. For the insertion of NaOH also by substitution of one water molecule, it is found that OH⁻ ions remain in solution close to the Na⁺ ions, forming ion pairs or chains. Depending on the number of water molecules present, the sodium ions are bi-, tri- or tetra-coordinated. Finally, some aspects concerning corrosion have been highlighted.     

晶体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱研究

在强场耦合图像中,采用双自旋-轨道耦合(SO)参量模型建立了过渡族3d2(3d8)离子的三角对称下全组态光谱能级和电子顺磁共振(EPR)公式.与经典的晶体场理论(仅考虑中心金属离子的自旋-轨道耦合作用)相比较,该公式还包括了配体离子的自旋-轨道耦合作用的贡献,这一模型在应用于计算共价性较强的晶体光谱和电子顺磁共振谱可得到合理的结果.作为验证,用完全对角化方法研究了品体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱,结果表明,理论与实验很好地符合.建立的全组态谱能级和电子顺磁共振公式为更精确地计算光谱和电子顺磁共振谱提供了一条可行方法.     

Stability,electronic structure,and optical properties of lead-free perovskite monolayer Cs3B2X9(B=Sb,Bi;X=Cl,Br,I)and bilayer vertical heterostructure Cs3B2X9/Cs3B’2X9(B,B’=Sb,Bi;X=Cl,Br,I)

The lead-free perovskites Cs₃B₂X₉(B=Sb,Bi;X=Cl,Br,I)as the popular photoelectric materials have excellent optical properties with lower toxicity.In this study,we systematically investigate the stable monolayer Cs₃B₂X₉and bilayer vertical heterostructure Cs₃B₂X₉/Cs3B02X9(B,B0=Sb,Bi;X=Cl,Br,I)via first-principles simulations.By exploring the electrical structures and band edge positions,we find the band gap reduction and the band type transition in the heterostructure Cs₃B₂X₉/Cs3B02X9 due to the charge transfer between layers.Furthermore,the results of optical properties reveal light absorption from the visible light to UV region,especially monolayer Cs3Sb2I9 and heterostructure Cs3Sb2I9/Cs3Bi2I9,which have absorption peaks in the visible light region,leading to the possibility of photocatalytic water splitting.These results provide insights for more two-dimensional semiconductors applied in the optoelectronic and photocatalytic fields.