The structures of four isomeric forms of the model germylenoid, H2GeLiF. have been examined by ah initio MO theory. The most stable structure is suggested to be the p-complex 1.The other three species. three-membered ...The structures of four isomeric forms of the model germylenoid, H2GeLiF. have been examined by ah initio MO theory. The most stable structure is suggested to be the p-complex 1.The other three species. three-membered ring 2, δ-complex 3 and tetrahedron 4. are also local minima on the potential energy surface. but are higher in energy.展开更多
Using gcomctrical optimization and DFT mcthod at thc B3LYP/6-311＋＋G （3dt,3pd） level, four equilibrium geometries and one transition state of GeHeLiCl were identified, and the structures at the MP2/6-311＋3G（3df,...Using gcomctrical optimization and DFT mcthod at thc B3LYP/6-311＋＋G （3dt,3pd） level, four equilibrium geometries and one transition state of GeHeLiCl were identified, and the structures at the MP2/6-311＋3G（3df,3pd） level were calculated simultaneously. We also sludied the solvent effects on the structures of Germylenoid GeH,LiCl at the B3LYP/6-311＋＋G （3dt,3pd） level. The two more stable forms are suggested to be the p-complex and three-membered ring. The vibrational frequencies and infrared intensities were computed at the B3LYP/6-311＋＋G （3df,3pd） level.展开更多
In the present work we investigated a novel triplet ground-state germylenoid HB=GeLiF as well as its insertion reactions with RH（R = F,OH and NH2） using the DFT B3LYP and QCISD methods for the first time.Geometry op...In the present work we investigated a novel triplet ground-state germylenoid HB=GeLiF as well as its insertion reactions with RH（R = F,OH and NH2） using the DFT B3LYP and QCISD methods for the first time.Geometry optimization calculations show that the triplet HB=GeLiF has three equilibrium structures,in which the four-membered ring structure is the most stable with the lowest energy.All mechanisms of the three insertion reactions of germylenoid HB=GeLiF with RH（R = F,OH,and NH2） are identical to each other.Based on the calculated results,it is concluded that under the same conditions the insertion reactions should occur easily in the order of H-F H-OH H-NH2.In THF solvent the insertion reactions get more difficult than in the gas phase.展开更多
The unsaturated germylenoid H2C=GeLiF has been studied by using DFT method at the B3LYP/6-311＋G （d, p） level. Geometry optimization calculations indicate that H2C=GeLiF has three equilibrium configurations, in whic...The unsaturated germylenoid H2C=GeLiF has been studied by using DFT method at the B3LYP/6-311＋G （d, p） level. Geometry optimization calculations indicate that H2C=GeLiF has three equilibrium configurations, in which the p-complex is the lowest in energy and the most stable structure. Two transition states for isomerization reactions of H2C=GeLiF are located and the energy barriers are calculated. For the most stable one, vibrational frequencies and infrared intensities have been predicted.展开更多
用密度泛函理论(DFT)和QCISD(quadratic configuration interaction with single and double excitations)方法研究了类锗烯H2GeClMgCl在气相和五种溶剂中的构型与异构化反应.结果表明,类锗烯H2GeClMgCl有三种平衡构型.其中p-配合物型...用密度泛函理论(DFT)和QCISD(quadratic configuration interaction with single and double excitations)方法研究了类锗烯H2GeClMgCl在气相和五种溶剂中的构型与异构化反应.结果表明,类锗烯H2GeClMgCl有三种平衡构型.其中p-配合物型构型能量最低,是其存在的主要构型.讨论了溶剂效应对结构、能量与异构化反应的影响.计算模拟了最稳定构型的红外光谱.展开更多
文摘The structures of four isomeric forms of the model germylenoid, H2GeLiF. have been examined by ah initio MO theory. The most stable structure is suggested to be the p-complex 1.The other three species. three-membered ring 2, δ-complex 3 and tetrahedron 4. are also local minima on the potential energy surface. but are higher in energy.
基金Supported by the Natural Science Foundation of Shandong Province (No. Y2003B03, Y2006B42) the Doctoral Foundation of Shandong Province (No. 2004BS04011)
文摘Using gcomctrical optimization and DFT mcthod at thc B3LYP/6-311＋＋G （3dt,3pd） level, four equilibrium geometries and one transition state of GeHeLiCl were identified, and the structures at the MP2/6-311＋3G（3df,3pd） level were calculated simultaneously. We also sludied the solvent effects on the structures of Germylenoid GeH,LiCl at the B3LYP/6-311＋＋G （3dt,3pd） level. The two more stable forms are suggested to be the p-complex and three-membered ring. The vibrational frequencies and infrared intensities were computed at the B3LYP/6-311＋＋G （3df,3pd） level.
基金Supported by the Natural Science Foundation of Shandong Province (ZR2009BQ006)the Fund for Doctor of Yantai University (HY05B30,HY05B36)the Open fund (SKLSSM200909) of the State Key Laboratory of Supramolecular Structure and Materials,Jilin University
文摘In the present work we investigated a novel triplet ground-state germylenoid HB=GeLiF as well as its insertion reactions with RH（R = F,OH and NH2） using the DFT B3LYP and QCISD methods for the first time.Geometry optimization calculations show that the triplet HB=GeLiF has three equilibrium structures,in which the four-membered ring structure is the most stable with the lowest energy.All mechanisms of the three insertion reactions of germylenoid HB=GeLiF with RH（R = F,OH,and NH2） are identical to each other.Based on the calculated results,it is concluded that under the same conditions the insertion reactions should occur easily in the order of H-F H-OH H-NH2.In THF solvent the insertion reactions get more difficult than in the gas phase.
基金Supported by NNSFC (20473029)the Fund for Doctor of Yantai University (HY05B30)the Open Project Program of Key Laboratory for Supramolecular Structure and Materials of Ministry of Education, Jilin University
文摘The unsaturated germylenoid H2C=GeLiF has been studied by using DFT method at the B3LYP/6-311＋G （d, p） level. Geometry optimization calculations indicate that H2C=GeLiF has three equilibrium configurations, in which the p-complex is the lowest in energy and the most stable structure. Two transition states for isomerization reactions of H2C=GeLiF are located and the energy barriers are calculated. For the most stable one, vibrational frequencies and infrared intensities have been predicted.
文摘用密度泛函理论(DFT)和QCISD(quadratic configuration interaction with single and double excitations)方法研究了类锗烯H2GeClMgCl在气相和五种溶剂中的构型与异构化反应.结果表明,类锗烯H2GeClMgCl有三种平衡构型.其中p-配合物型构型能量最低,是其存在的主要构型.讨论了溶剂效应对结构、能量与异构化反应的影响.计算模拟了最稳定构型的红外光谱.
