The HeI photoelectron (PE) spectra of both 2(5H) furanone and its trans-chair-dimenc-compound (t-c-DFN) are reported.The assignment of the PES bands is made on the basis of band shapes,the PES results of the molecules...The HeI photoelectron (PE) spectra of both 2(5H) furanone and its trans-chair-dimenc-compound (t-c-DFN) are reported.The assignment of the PES bands is made on the basis of band shapes,the PES results of the molecules which have the similar atomic groups,and the restricted Hartree-Fock (RHF) calculations for the molecules studied.From the results of both PES experimental and theoretical calculations,it is proved that the ionization potential (IPs) of the HOMO for the dimenc-compound is lower than that of the HOMO for the monomer.And the total energy computed for the t-c-DFN is the lowest in the four possible configurations of dimeric-compounds of 2(5H) furanone Therefore the synthesis of t-c-DFN is also the easiest.展开更多
由于拥有―C(O)S―和―NCO基团,FC(O)SNCO的分子和电子结构是非常有趣的.利用FC(O)SCl和Ag NCO制备了FC(O)SNCO,并利用He I光电子能谱(PES)、光电离质谱(PIMS)以及理论计算研究了其分子和电子结构.通过将实验、理论计算以及自然键轨道(N...由于拥有―C(O)S―和―NCO基团,FC(O)SNCO的分子和电子结构是非常有趣的.利用FC(O)SCl和Ag NCO制备了FC(O)SNCO,并利用He I光电子能谱(PES)、光电离质谱(PIMS)以及理论计算研究了其分子和电子结构.通过将实验、理论计算以及自然键轨道(NBO)分析结合起来,获得了FC(O)SNCO的最稳定分子构型.利用外壳层格林函数(OVGF)方法以及与相似化合物的比较,对其光电子能谱进行了指认.理论计算表明,对于中性分子最稳定的构型为syn-syn非平面构型,而电离后的离子最稳定构型为syn-syn平面构型.实验结果表明,第一电离能来自于S的孤对电子轨道,为10.33 e V.第二至第六电离能分别为12.03、13.23、13.77、14.78、15.99 e V,并对这些电离能进行了指认.在光电离质谱中产生了六个质谱峰,分别为SN+、FC(O)+、SNCO+、FC(O)SN+、C(O)SNCO+、FC(O)SNCO+,其中FC(O)SNCO+的峰是最强峰.结合HeI光电子能谱和理论计算,对PIMS进行了分析,并研究了可能的电离和解离过程并对其进行了讨论.展开更多
HeI photoelectron spectra of w-heterocycle a-cyano polyenic ethyl ester compounds (1-6) have been given in this paper. Assignment of the spectra is also done with the aid of HeI photoelectron spectroscopic (PES) resul...HeI photoelectron spectra of w-heterocycle a-cyano polyenic ethyl ester compounds (1-6) have been given in this paper. Assignment of the spectra is also done with the aid of HeI photoelectron spectroscopic (PES) results of smaller molecules which have similar atomic group to the molecules studied, and the aid of MNDO molecules orbital calculations. The lowest PES experimental ionization potentials (IPs in eV) of different molecules reduce gradually with the increasing number of ethylenic group. The -CO2C2H5 group can be only considered as a substituent.展开更多
HeI photoelectron spectrum of B(OCH3)3 is presented in this paper. The assignment of the spectrum has been also done by an analysis of the intensity of the spectrum bands and the optimized MNDO molecular orbital calcu...HeI photoelectron spectrum of B(OCH3)3 is presented in this paper. The assignment of the spectrum has been also done by an analysis of the intensity of the spectrum bands and the optimized MNDO molecular orbital calculation on B(OCH3)3 molecule. The split showing a 1.08eV of the bands at the lowest two ionization potentials (IPs) was assigned to the Jahn-Teller split of the doubly degenerate oxygen lone-pair orbitals. And the splits showing 0.42eV and 0.38eV on the above-mentioned hands were considered as the result of spin-orbital interaction. Therefore the this PES study provides an exceedirlgly experimental example to testify the Jahn-Teller effect and the spin-orbital interaction splitting.展开更多
1 Introduction It has been known from the experiment that two conjugated systems of aromaticheterocyclic carbonyl and phenyl carbonyl groups in the aromatic heterocylic phenylketone compounds are not equivalent and so...1 Introduction It has been known from the experiment that two conjugated systems of aromaticheterocyclic carbonyl and phenyl carbonyl groups in the aromatic heterocylic phenylketone compounds are not equivalent and so are not coplanary. The synhesis展开更多
The phenyl polyenic phenyl ketones (shown as below) belong to the forkedconjugative compounds.It is united, through an atom or a group, by three conjugated groups or three conju-gated bonds. Many compounds consisting ...The phenyl polyenic phenyl ketones (shown as below) belong to the forkedconjugative compounds.It is united, through an atom or a group, by three conjugated groups or three conju-gated bonds. Many compounds consisting of the carbonyl group and aromatic ringare typical forked conjugative compounds.展开更多
Due to special properties of transient species,such as short-lived,unstable,reactive,and even explo-sive,the generation and subsequent characterization is a great challenge for experimental chemists. In our laboratory...Due to special properties of transient species,such as short-lived,unstable,reactive,and even explo-sive,the generation and subsequent characterization is a great challenge for experimental chemists. In our laboratory,systematic researches have been carried out to investigate novel transient species:reactive halogen species(RHS) ,short-lived free radicals,and metastable pseudohalogen compounds,based on the successive technical improvements on the HeI Photoelectron spectroscopy(PES) . In this review,the topic mainly focuses on innovative methods of generating novel transient species,and subsequent geometric and electronic structure characterizations of these species combined with quantum chemical calculations.展开更多
基金Project supported by the National Natural Science Foundation of China
文摘The HeI photoelectron (PE) spectra of both 2(5H) furanone and its trans-chair-dimenc-compound (t-c-DFN) are reported.The assignment of the PES bands is made on the basis of band shapes,the PES results of the molecules which have the similar atomic groups,and the restricted Hartree-Fock (RHF) calculations for the molecules studied.From the results of both PES experimental and theoretical calculations,it is proved that the ionization potential (IPs) of the HOMO for the dimenc-compound is lower than that of the HOMO for the monomer.And the total energy computed for the t-c-DFN is the lowest in the four possible configurations of dimeric-compounds of 2(5H) furanone Therefore the synthesis of t-c-DFN is also the easiest.
基金supported by the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(XDB05010400)National NaturalScience Foundation of China(41105085,21073051)Natural Science Foundation of Hebei Province,China(B2010000368)~~
文摘由于拥有―C(O)S―和―NCO基团,FC(O)SNCO的分子和电子结构是非常有趣的.利用FC(O)SCl和Ag NCO制备了FC(O)SNCO,并利用He I光电子能谱(PES)、光电离质谱(PIMS)以及理论计算研究了其分子和电子结构.通过将实验、理论计算以及自然键轨道(NBO)分析结合起来,获得了FC(O)SNCO的最稳定分子构型.利用外壳层格林函数(OVGF)方法以及与相似化合物的比较,对其光电子能谱进行了指认.理论计算表明,对于中性分子最稳定的构型为syn-syn非平面构型,而电离后的离子最稳定构型为syn-syn平面构型.实验结果表明,第一电离能来自于S的孤对电子轨道,为10.33 e V.第二至第六电离能分别为12.03、13.23、13.77、14.78、15.99 e V,并对这些电离能进行了指认.在光电离质谱中产生了六个质谱峰,分别为SN+、FC(O)+、SNCO+、FC(O)SN+、C(O)SNCO+、FC(O)SNCO+,其中FC(O)SNCO+的峰是最强峰.结合HeI光电子能谱和理论计算,对PIMS进行了分析,并研究了可能的电离和解离过程并对其进行了讨论.
基金Project supported by the National Natural Science Foundation of China.
文摘HeI photoelectron spectra of w-heterocycle a-cyano polyenic ethyl ester compounds (1-6) have been given in this paper. Assignment of the spectra is also done with the aid of HeI photoelectron spectroscopic (PES) results of smaller molecules which have similar atomic group to the molecules studied, and the aid of MNDO molecules orbital calculations. The lowest PES experimental ionization potentials (IPs in eV) of different molecules reduce gradually with the increasing number of ethylenic group. The -CO2C2H5 group can be only considered as a substituent.
文摘HeI photoelectron spectrum of B(OCH3)3 is presented in this paper. The assignment of the spectrum has been also done by an analysis of the intensity of the spectrum bands and the optimized MNDO molecular orbital calculation on B(OCH3)3 molecule. The split showing a 1.08eV of the bands at the lowest two ionization potentials (IPs) was assigned to the Jahn-Teller split of the doubly degenerate oxygen lone-pair orbitals. And the splits showing 0.42eV and 0.38eV on the above-mentioned hands were considered as the result of spin-orbital interaction. Therefore the this PES study provides an exceedirlgly experimental example to testify the Jahn-Teller effect and the spin-orbital interaction splitting.
文摘1 Introduction It has been known from the experiment that two conjugated systems of aromaticheterocyclic carbonyl and phenyl carbonyl groups in the aromatic heterocylic phenylketone compounds are not equivalent and so are not coplanary. The synhesis
文摘The phenyl polyenic phenyl ketones (shown as below) belong to the forkedconjugative compounds.It is united, through an atom or a group, by three conjugated groups or three conju-gated bonds. Many compounds consisting of the carbonyl group and aromatic ringare typical forked conjugative compounds.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 2880168,27170306,49392703, 29673049, 29973051, 20073052,50372071,20473094, 20477047, 20577052 and 20673123)the Chinese Academy of Sciences (Hundred Talents Fund)+1 种基金 Knowledge Innovation Program of the Chinese Acad-emy of Sciences (Grant Nos. KJCX2-H2, KJCX2-SW-H8 and KZCX2-YW-205)973 Program, Ministry of Science and Technology of China (Grant No. 2006CB403701)
文摘Due to special properties of transient species,such as short-lived,unstable,reactive,and even explo-sive,the generation and subsequent characterization is a great challenge for experimental chemists. In our laboratory,systematic researches have been carried out to investigate novel transient species:reactive halogen species(RHS) ,short-lived free radicals,and metastable pseudohalogen compounds,based on the successive technical improvements on the HeI Photoelectron spectroscopy(PES) . In this review,the topic mainly focuses on innovative methods of generating novel transient species,and subsequent geometric and electronic structure characterizations of these species combined with quantum chemical calculations.
