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71.
The C–H homolytic bond dissociation enthalpies (BDEs) of 27 heterocyclic compounds of small systems (less than 8 non-hydrogen atoms) were evaluated by the composite ab initio methods of G4 and CBS-Q. In addition, the C–H BDEs of an extended database including 60 heterocyclic compounds were assessed by 16 DFT functionals. The correlation between the theoretical and experimental values reveals that the BMK functional provided the lowest root mean square error (RMSE) of 10.2 kJ/mol, and the correlation coefficient (R2) was 0.955. The mean deviation (MD), mean absolute deviation (MAD) of BMK are 0.1 kJ/mol and 7.9 kJ/mol separately. Therefore, we utilized BMK to research C–H BDEs together with the substituent effects of five-membered and six-membered heterocyclic compounds including large systems. The nature of C–H BDE change pattern was analyzed by the natural bond orbital (NBO). 相似文献
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Jianjun Chen Chengwei Sun Kexiu Rong Hongyun Li Qihuang Gong 《Laser \u0026amp; Photonics Reviews》2015,9(4):419-426
Surface plasmon polaritons (SPPs) have sparked enormous interest on nanophotonics beyond the diffraction limit for their remarkable capabilities of subwavelength confinements and strong enhancements. Due to the inherent polarization sensitivity of the SPPs [transverse‐magnetic (TM) polarization], it is a great challenge to couple the s‐polarized free‐space light to the SPPs. Here, an ultrasmall defect aperture (<λ2/2) is designed to directionally couple both the p‐ and s‐polarized incident beams to the single SPP mode in a broad bandwidth, which is guided by a subwavelength plasmonic waveguide. Simulations show that hot spots emerge at the sharp corners of the defect aperture when the incident beams illuminate it from the back side. The strong radiative fields from the hot spots are directionally coupled to the SPP mode because of the symmetry breaking of the defect aperture. By adjusting the structural parameters, both the unidirectional and bidirectional SPP coupling from the two orthogonal linear‐polarization incident beams are experimentally demonstrated. The polarization‐free coupling of the SPPs is of importance in circuits for fully optical processing of information with a deep‐subwavelength footprint.
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本文研究了Hanski et al(1991)提出的生态学模型dx/dt=r0x(1-x/k)-cxy/d+x-gx2/(h2+x2);dy/dt=s0y(1-qy/x)。对捕食者既有HollingⅡ型功能性反应,又有HollingⅢ型功能性反应,对食饵来说既有广食者又有专食者,本文将分析Hanski et al(1991)提出的模型的平衡点、极限环和全局渐近稳定性等动力学行为。 相似文献
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1 Introduction TheconventionalMach Zehnderinterferometerisanimportantdiagnostictool.Frequentlyusedinthefieldsofplasmaphysics,aerodynamics,andheattransferformeasuringdensity ,pressure ,andtemperaturechangesingases.Becauseofitsrelativelylargeandfreelyacces… 相似文献
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用瓜类刺盘孢(Colletotrichum lagenarium)孢子悬液及其液体培养滤液提取物(简称El)和菌丝壁提取物(简称Ew)分别对哈密瓜黄化苗进行诱导处理,其可溶性总糖、蔗糖、果糖、淀粉含量及其相关的蔗糖酶和淀粉酶都有不同程度的变化,并且绿原酸在诱导处理一定时间后也有明显积累。其诱导效果用孢子悬液显著高于用El和Ew处理。 相似文献
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1 Introduction Long periodfiber gratings (LPGs )recentlyattractedmuchattentionforuseinopticalsensingapplications[1,2 ] .Theyareusedassensingcomponentstomeasuretemperature ,strainandbendingoffiber .However ,minimizingthecrosstalkbetweendifferentmeasurands,espec… 相似文献
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A series of iridium tetrahydride complexes [Ir(H)4(PSiP‐R)] bearing a tridentate pincer‐type bis(phosphino)silyl ligand ([{2‐(R2P)C6H4}2MeSi]−, PSiP‐R, R=Cy, iPr, or tBu) were synthesized by the reduction of [IrCl(H)(PSiP‐R)] with Me4N ⋅ BH4 under argon. The same reaction under a nitrogen atmosphere afforded a rare example of thermally stable iridium(III)–dinitrogen complexes, [Ir(H)2(N2)(PSiP‐R)]. Two isomeric dinitrogen complexes were produced, in which the PSiP ligand coordinated to the iridium center in meridional and facial orientations, respectively. Attempted substitution of the dinitrogen ligand in [Ir(H)2(N2)(PSiP‐Cy)] with PMe3 required heating at 150 °C to give the expected [Ir(H)2(PMe3)(PSiP‐Cy)] and a trigonal bipyramidal iridium(I)–dinitrogen complex, [Ir(N2)(PMe3)(PSiP‐Cy)]. The reaction of [Ir(H)4(PSiP‐Cy)] with three equivalents of 2‐norbornene (nbe) in benzene afforded [IrI(nbe)(PSiP‐Cy)] in a high yield, while a similar reaction of [Ir(H)4(PSiP‐R)] with an excess of 3,3‐dimethylbutene (tbe) in benzene gave the C H bond activation product, [IrIII(H)(Ph)(PSiP‐R)], in high yield. The oxidative addition of benzene is reversible; heating [IrIII(H)(Ph)(PSiP‐Cy)] in the presence of PPh3 in benzene resulted in reductive elimination of benzene, coordination of PPh3, and activation of the C H bond of one aromatic ring in PPh3. [IrIII(H)(Ph)(PSiP‐R)] catalyzed a direct borylation reaction of the benzene C H bond with bis(pinacolato)diboron. Molecular structures of most of the new complexes in this study were determined by a single‐crystal X‐ray analysis. 相似文献