有机锡配合物{[n-Bu_2Sn(O_2CC_5H_3NCl)]_2O}_2的合成、结构及量子化学研究

二正丁基氧化锡和2-氯-3-吡啶甲酸反应,合成2-氯-3-吡啶甲酸二正丁基锡配合物{[n-Bu2Sn(O2CC5H3NCl]2O}2.经X-射线衍射法测定了晶体结构.晶体属三斜晶系,空间群P-1,晶体学参数a=1.17841(9)nm,b=1.20811(9)nm,c=2.7460(2)nm,α=80.5330(10)°,β=84.1140(10)°,γ=64.2450(10)°,Z=2,V=3.4709(5)nm3,Dc=1.521 mg·m-3,μ(MoKa)=1 628 mm-1,F(000)=1592,R1=0.0430,wR2=0.1005.化合物是以Sn2O2构成的平面四元环为中心环的二聚体结构,锡原子均为五配位的畸变三角双锥形.用量子化学从头计算其结构,探讨配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征.     

四(邻羟基苄基)锡的合成、晶体结构和量子化学研究

邻氯甲基苯酚与锡反应合成了四(邻羟基苄基)锡,经X-射线方法测定其晶体结构.晶体属四方晶系,空间群为,I4(1)/a,晶体学参数:a=1.96881(18)nm,b=1.96881(18)nm,c=O.59392(8)nm,V=2.3022(4)nm3,Z=4,Dx=1.567g/cm3μ(Mo Kα)=11.43 cm-1,F(000)=1096,RI=0.0240,wR2=O.0642.中心锡原子与亚甲基碳原子构成畸型四面体.从头计算分子结构的量子化学.探讨化合物的稳定性、分子轨道能量、原子净电荷布居规律以及一些前沿分子轨道的组成特征.     

有机锡化合物[p-CNC_6H_4CH_2)_2Sn(H_2O)Cl_2]·2H_2O的合成、晶体结构和量子化学研究

对氰基氯化苄与锡粉在含水甲苯中反应,直接合成了标题化合物,经元素分析、~1HNMR、IR和X-线衍射表征分子结构,该化合物晶体学参数:单斜晶系,空间群P2_1/c,a=1.56495(7)nm,b=0.95703(4)nm,c=2.58692(12)nm,β=104.579(3)°,Z=4,V=3.7497(3)nm~3,D_c=1.686Mg·m~(-3),μ(MoK_a)1.664mm~(-1),F(000)=1888,R=0.0424,wR=0.1003;中心原子呈五配位三角双锥构型。利用量子化学G03W程序,在Lan12dz基组,对化合物的稳定性、分子轨道能量、原子净电荷布居及前沿分子轨道组成进行了研究;结果表明:化合物结构分析与量子化学计算结果一致,量化计算的方法可为有机锡化合物的设计和分子组装提供参考。     

镍(Ⅱ)配合物[Ni(Hpydc)_2]·3(H_2O)的合成结构和量子化学研究

氯化镍与吡啶-2,6-二甲酸(H_2pydc)反应,合成六配位镍配合物[Ni(Hpydc)_2]·3(H_2O),经元素分析、IR和X-射线衍射表征分子结构,该化合物晶体学参数:单斜晶系,空间群P2(1)/n,晶体学数据:a=1.36774(14)nm,b=1.00348(10)nm,c=1.375 87(14)nm,β=115.135 0(10)°,V=1.7096(3)nm~3,Z=4,Dc=1.729 g/cm~3,μ,(MoKα)=1.202 cm~(-1),F(000)=912,R_1=0.0362,wR_2=0.093 3[对I>2σ(I)的衍射]和R_1=0.0510,wR_2=0.1004(对所有的衍射)。共收集9064个数据,其中独立衍射点3018个,可观察衍射[I>2σ(I)]点2293个用于结构精修。配合物的Ni(Ⅱ)原子关于配基原子形成变形八面体。利用量子化学G98W软件,在Lan12dz基组对配合物的稳定性、前沿分子轨道组成及能量进行研究。     

铜(Ⅱ)配合物[Cu(pydc)(H2O)2]2合成、结构和量子化学的研究

合成标题配合物[Cu(pydc)(H2O)2]2(pyde=吡啶-2,6-二甲根),经元素分析、IR和X-射线衍射表征,该配合物晶体属三斜晶系,空间群P1,晶胞参数:a=0.47166(11)nm,b=0.8973(2)nm,c=1.0337(2)am,α=81.120(3)°,β=85.755(3)°,γ=83.352(3)°,V=0.42865(17)nm3,Z=1,Dc=2.051 g/cm3,μ(MoKα)=25.57 mm-1,F(000)=266,and R1=0.0250,wR2=0.0631[对I>2σ(I)的衍射]和R1=0.0313,wR2=0.0651(对所有的衍射).共收集数据2350个,其中独立衍射点1498个,可观察衍射[I>2σ(I)]点1311个用于结构精修.中心Cu原子与配基原子形成变形四棱锥,分子间通过氢键作用形成三维网络结构.利用量子化学G98W程序,在Lanl2dz基组研究配合物的稳定性、前沿分子轨道组成及能量.     

铜配合物[Cu(AFO)2]2(SO4)的合成、结构和量子化学研究

硫酸铜与4,5-二氮芴-9-酮(AFO)反应合成四配位铜配合物[Cu(AFO)2]2(SO4),并经元素分析、IR和X-射线衍射表征分子结构,该化合物晶体学参数:单斜晶系,空间群P2(1)/c,晶体学数据:a=0.78885(14)nm,b=1.3358(2)nm,c=1.9292(3)nm,β=96.179(3)°,V=1.7096(3)nm3,Z=4,Dc=1.722 g/cm3,μ(MoKa)=1.236 cm-1,F(000)=1060,R1=0.0437,wR2=0.1225[对I＞2o(1)的衍射]和R1=0.0634,wR2=0.1362(对所有的衍射).共收集10795个数据,其中独立衍射点3576个,可观察衍射[1＞2o(1)]点2553个用于结构精修.配合物的铜原子关于配基原子形成变形平面四方型.利用量子化学G98W软件,在Lan12dz基组对配合物的稳定性、前沿分子轨道组成及能量进行了研究.     

二聚有机锡配合物[（n-Bu）2Sn（H2O）C5H3N（CO2）2]2的合成、结构和量子化学研究

吡啶-2,6-二甲酸与(n-Bu)2SnO反应合成标题化合物,并经元素分析、IR和X-射线衍射表征,该配合物晶体属四方晶系,空间群P42/n,晶胞参数:a=1.77103(6)nm,b=1.77103(6)nm,c=1.11717(7)nm,α=90°,β=90°,γ=90°,V=3.5041(3)nm3,Z=4,Dc=1.577g/cm3,μ(MoKα)=1.479mm-1,F(000)=1680andR1=0.0329,wR2=0.0852[对I>2σ(I)的衍射]和R1=0.0428,wR2=0.0937(对所有的衍射)。共收集12600个数据,其中独立衍射点3431个,可观察衍射[I>2σ(I)]点2723个用于结构精修。中心Sn原子形成七配位变形十面体,分子间通过氧原子的氢键作用形成三维网络结构。利用量子化学G98W软件,在Lanl2dz基组对化合物的稳定性、前沿分子轨道组成及能量进行研究。     

四水二(吡啶-4-甲酸)合铜配合物的合成、晶体结构和量子化学研究

铜(Ⅱ)盐与吡啶-4-甲酸水溶液合成标题配合物,并经元素分析、IR和X-射线衍射表征,该配合物晶体属三斜晶系,空间群P-1,晶胞参数:α=0.6310(3)nm,b=0.6906(3)nm,c=0.9234(6)nm,α=96.312(19)°,β=105.26(2)°,γ=113.353(14)°,V=0.3458(3)nm3,Z=1,Dc=1.824g/cm3,μ(MoKα)=1.627mm-1,F(000)=195,and R=0.0360,wR2=0.1051[对I>2σ(I)的衍射]和R1=0.0361,wR2=0.1051(对所有的衍射).共收集1803个数据,其中独立衍射点1226个,可观察衍射[I>2σ-(I)]点1223个用于结构精修.中心Cu原子关于配基原子形成变形八面锥,分子间通过氢键作用形成三维网络结构.利用量子化学G98W程序,在Lan12dz基组对配合物的稳定性、前沿分子轨道组成及能量进行研究.     

配合物[n-BuSnCl_3(phen)]的合成、晶体结构及量化计算

丁基三氯化锡与1,10-邻菲罗啉反应,合成了标题配合物,经元素分析、~1H NMR和IR表征,通过X射线衍射方法测定了化合物的晶体结构。该化合物晶体学参数:三斜晶系,空间群为P1,晶胞参数:a=0.67605(6)mm,b=0.93673(9)nm,c=1.37116(13)nm,Z=2,V=0.86474(14)nm~3,D_c=1.766 g·cm~(-3),μ(MoK_α)=1.938mm~(-1),F(000)=456,R_1=0.0366,wR_2=0.0818;中心锡原子呈六配位畸变八面体构型。利用量子化学G98W软件,在Lanl2dz基组对化合物的稳定性、前沿分子轨道组成及能量进行研究。     

Synthesis, crystal structure and quantum chemistry of the organooxotin cluster [(n-Bu)2Sn(H2O)CsH3N(CO2)2]2

吡啶-2,6-二甲酸与(n-Bu)2SnO反应合成标题化合物,并经元素分析、IR和X-射线衍射表征,该配合物晶体属四方晶系,空间群P42/n,晶胞参数:a=1.77103(6) nm,b=1.77103(6) nm,c=l.11717(7) nm,α=90°,β=90°,γ=90°,V=3.5041(3) nm3,Z=4,Dc=1.577g/cm3,μ(MoKα)=1.479mm-1,F(000)=1680 and R1=0.0329,wR2=0.0852[对I＞ 2σ(I)的衍射]和R1=0.0428,wR2=0.0937(对所有的衍射).共收集12600个数据,其中独立衍射点3431个,可观察衍射[I＞2σ(I)]点2723个用于结构精修.中心Sn原子形成七配位变形十面体,分子间通过氧原子的氢键作用形成三维网络结构.利用量子化学G98W软件,在Lan12dz基组对化合物的稳定性、前治分子轨道组成及能量进行研究.     

Microstructural,dielectric and piezoelectric properties of low-temperature sintering Pb(Co1/2W1/2)O3–Pb(Mn1/2Nb2/3)O3–Pb(Zr,Ti)O3 ceramics with the addition of Li2CO3 and Bi2O3

In this study, in order to develop the low-temperature sintering ceramics for multilayer piezoelectric devices, Pb(Co_1/2W_1/2)O₃–Pb(Mn_1/2Nb_2/3)O₃–Pb(Zr,Ti)O₃ (PCW–PMN–PZT) ceramics doped with Li₂CO₃, Bi₂O₃ and CuO as sintering aids were manufactured, and their microstructural, dielectric and piezoelectric properties were investigated. When the only CuO was added, specimens could not be sintered below 980 °C. However, when Li₂CO₃ and Bi₂O₃ with CuO were simultaneously added to the basic composition ceramics, specimens could be sintered below 980 °C. The addition of Li₂CO₃ and Bi₂O₃ were proved to lower sintering temperature of piezoelectric ceramics due to the effect of Li₂CO₃–Bi₂O₃ liquid phase. Piezoelectric properties of Li₂CO₃ and Bi₂O₃ added specimens showed higher values than those of the only CuO added specimens. At 0.2 wt% Li₂CO₃ and 0.3 wt% Bi₂O₃ added specimen sintered at 920 °C, the dielectric constant (ɛ_r) of 1457, electromechanical coupling factor (k_p) of 0.56 and mechanical quality factor (Q_m) of 1000 were shown, respectively. It is considered that these values are suitable for piezoelectric device application such as multilayer piezoelectric transformer and ultrasonic vibrator with pure Ag internal electrode.     

C3N3(NH2)3、[C(O)NH]3和水双分子间的氢键相互作用

采用密度泛函理论,在B3LYP/6-311+G**水平上对C3N3(NH2)3、[C(O)NH]3、H2O 3种单体在气相中形成的双分了氢键作用体系进行构型优化和频率计算.通过几何优化得到一系列含多个氢键的复合物.频率分析表明,与单体相比,体系形成氢键作用后,参与氢键形成相关的键的红外谱带位置和振动强度都发生明显的变化,其中C3N3(NH2)3-[C(O)NH]3体系中N8-H9键的红移最明显.同时,通过B3LYP/6-311+G**和MP2/6-311+G**水平计算的含基组重叠误差(BSSE)校正的氢键相互作用能分析表明,C3N3(NH2)3-[C(O)NH]3氢键体系的相互作用能最大,其次是([C(O)NH]3)2体系,采用MP2/6-311+G**方法计算的相互作用能分别达到-14.171 kcal·mol-1和-10.217 kcal·mol-1.另外,通过自然键轨道理论揭示氢键相互作用的本质.     

Theoretical investigation on gas-phase reaction of CF3CH2OCH3 with OH radicals and fate of alkoxy radicals (CF3CH(O)OCH3/CF3CH2OCH2O)

Detailed theoretical investigation has been performed on the mechanism, kinetics and thermochemistry of the gas phase reactions of CF₃CH₂OCH₃ (HFE-263fb2) with OH radicals using ab-initio and DFT methods. Reaction profiles are modeled including the formation of pre-reactive and post-reactive complexes at entrance and exit channels, respectively. Our calculations reveal that hydrogen abstraction from the CH₂ group is thermodynamically and kinetically more facile than that from the CH₃ group. Using group-balanced isodesmic reactions, the standard enthalpies of formation for CF₃CH₂OCH₃ and radicals (CF₃CHOCH₃ and CF₃CH₂OCH₂) are also reported for the first time. The calculated bond dissociation energies for the CH bonds are in good agreement with experimental results. At 298 K, the calculated total rate coefficient for CF₃CH₂OCH₃ + OH reactions is found to be in good agreement with the experimental results. The atmospheric fate of the alkoxy radicals, CF₃CH(O)OCH₃ and CF₃CH₂OCH₂O are also investigated for the first time using the same level of theory. Out of three plausible decomposition channels, our results clearly point out that reaction with O₂ is not the dominant path leading to the formation of CF₃C(O)OCH₃ for the decomposition of CF₃CH(O)OCH₃ radical in the atmosphere. This is in accord with the recent report of Osterstrom et al. [CPL 524 (2012) 32] but found to be in contradiction with experimental finding of Oyaro et al. [JPCA 109 (2005) 337].     

配合物{Cu[PHBA]2(H2O)3}(H2O)3的水热合成、晶体结构、电化学分析及量化计算

在甲醇和水的混合溶剂中通过水热反应,以对羟基苯甲酸和4,4′-联吡啶为配体合成了配合物{Cu[PHBA]_2(H_2O)_3} (H_2O)_3,并测定了配合物的晶体结构,该晶体属三斜晶系,空间群c2(1),晶胞参数为:a=2.4428(5)nm,b=1.14476(17)nm,c=0.72516(11)nm,α=β=γ=90.00°,V=2.0278(6)nm~3,Dc=1.578g/cm~3,Z=4,F(000)=1004。最终偏离因子R_1= 0.0304,wR_2=0.0796。配合物中Cu(Ⅱ)离子与2个对羟基苯甲酸的2个羧基O原子及3个水分子中的3个氧原子配位,形成三角双锥结构,铜位于结构中心。结合晶体结构对配合物进行了电化学性质分析和量子化学计算。     

Programs for generating Clebsch-Gordan coefficients of SU(3) in SU(2) and SO(3) bases

Computer codes are developed to calculate Clebsch-Gordan coefficients of SU(3) in both SU(2)- and SO(3)-coupled bases. The efficiency of this code derives from the use of vector coherent state theory to evaluate the required coefficients directly without recursion relations. The approach extends to other compact semi-simple Lie groups. The codes are given in subroutine form so that users can incorporate the codes into other programs.

Program summary

Title of program: SU3CGVCSCatalogue identifier: ADTNProgram summary URL:http://cpc.cs.qub.ac.uk/summaries/ADTNProgram obtainable from: CPC Program Library, Queen's University of Belfast, N. IrelandLicensing provisions: Persons requesting the program must sign the standard CPC non-profit use licenseComputers for which the program is designed and others on which it is operable: SGI Origin 2000, HP Apollo 9000, Sun, IBM SP, PentiumOperating systems under which the program has been tested: IRIX 6.5, HP UX 10.01, SunOS, AIX, LinuxProgramming language used: FORTRAN 77Memory required to execute with typical data: On the HP system, it requires about 732 KBytes.Disk space used for output: 2100+2460 bytesNo. of bits in a word: 32 bit integer and 64 bit floating point numbers.No. of processors used: 1Has the code been vectorized: NoNo. of bytes in distributed program, including test data, etc.: 26 309No. of lines in distributed program, including test data, etc.: 3969Distribution format: tar gzip fileNature of physical problem: The group SU(3) and its Lie algebra have important applications, for example, in elementary particle physics, nuclear physics, and quantum optics [1-3]. The code presented is particularly relevant for the last two fields. Clebsch-Gordan (CG) coefficients are required whenever the symmetries of many-body systems are used for the evaluation of matrix elements of tensor operators. Moreover, the construction of CG coefficients for SU(3) serves as a nontrivial prototype for larger compact semi-simple Lie algebras and even for non semi-simple Lie algebras. It is the simplest Lie algebra to have multiplicity in its outer products and a non-canonical subalgebra, i.e., SO(3).Method of solution: Vector coherent state theory is first used to construct bases for the products of two irreducible representations (irreps) [4]. The bases are SU(2)-coupled so that SU(2)-reduced CG (or isoscalar factors) can be constructed naturally. The CG coefficients in the SO(3) bases are constructed subsequently from the overlaps between the SU(2) and SO(3) bases.Restriction on the complexity of the problem: The programs are limited by computer memory and the maximum size of variable arrays. As dimension overflow conditions are possible, they are flagged and can be fixed by following the directions given as part of the error message.Typical running time: The calculation time for a single SU(3) CG coefficient is very different for SU(2) and SO(3) bases. It varies between 7.3-54.1 ns in SGI Origin 2000, 0.81-5.48 ms in HP Apollo 9000, or 0.055-0.373 ms in Intel Pentium 4 for SU(2) bases while it is between 0.027-0.255 s in Intel Pentium 4 for SO(3) bases.Unusual features of the program: Intrinsic bit functions: and, or, and shift, called iand, ior, and ishft, respectively, in FORTRAN, are used for packing and unpacking the labels for the irreps. Intrinsic logical btest is used to test the bit for the phase factor.References:[1] Y. Ne'eman, Nucl. Phys. 26 (1961) 222;  M. Gell-Man, Y. Ne'eman, The Eightfold Way, Benjamin, New York, 1964.[2] J.P. Elliott, Proc. Roy. Soc. A 245 (1958) 128, 562.[3] M. Reck, A. Zeilinger, H.J. Bernstein, P. Bertani, Phys. Rev. Lett. 73 (1994) 58;  B.C. Sanders, H. de Guise, D.J. Rowe, A. Mann, J. Phys. A 32 (1999) 7111.[4] D.J. Rowe, C. Bahri, J. Math. Phys. 41 (2000) 6544.     

Thermodynamic modeling of the Ca(NO3)2-MNO3 (M: alkali metal) systems

This work presents a thermodynamic evaluation of the Ca(NO₃)₂-MNO₃ (M: Li, Na, K, Rb, Cs) binary systems using the CALPHAD approach. The required Gibbs energy of liquid Ca(NO₃)₂ is missing in the literature and has been successfully evaluated in the present work with a fusion enthalpy of 23849 J mol⁻¹. The substitutional solution model can thus be employed to describe the Ca(NO₃)₂-base liquid phase. All the intermediate compounds are treated to be stoichiometric and their Gibbs energies comply with the Neumann-Kopp rule. Empirical functions relating mixing enthalpies to ionic parameters are employed to predict the corresponding values of binary melts which are used as input data to assist in parameters optimization for the liquid phases. The final calculated results show good agreement with most of the experimental and predicted data.