The reaction of methylene radicals in their 3 B1 electronic ground state with molecular NO was studied. Pure CH2(X 3 B1 ) radicals were prodced by UV photolysis of ketene at 351 nm.The products were measured by Time-R...The reaction of methylene radicals in their 3 B1 electronic ground state with molecular NO was studied. Pure CH2(X 3 B1 ) radicals were prodced by UV photolysis of ketene at 351 nm.The products were measured by Time-Resolved Fourier Transform Infrard (TR-FTIR) spectrometer. CO.OH .NH2 and HOCN or its isomer HNCO were found as primary prodcts and several possible channels of this reaction were suggested.展开更多
The ultrafast processes of tetra-phenyl-porphyrin(TPP), tetra-t-butyl-phthalocyanine(BuPc) and nitro-tri-t-butyl-phthalocyanine (NtBuPc) have been inves-tigated using the femtosecond time-resolved fluorescence depleti...The ultrafast processes of tetra-phenyl-porphyrin(TPP), tetra-t-butyl-phthalocyanine(BuPc) and nitro-tri-t-butyl-phthalocyanine (NtBuPc) have been inves-tigated using the femtosecond time-resolved fluorescence depletion method. A sharp peakof the fluorescence depletion with delay time has been observed both for TPP and BuPc.An ultrafast two-photon absorption process has been proposed to explain the sharp peakobserved. A long-lived fluorescence depletion has also been observed. It is causing by thestimulated-emission-pumping process produced by the intense probe laser pulses.展开更多
The vacuum ultraviolet photoionization spectrum of Si(CH3)2Cl2 has been obtained with synchrotron radiation source. The adiabatic iomzation potential of Si(CHa)2Cl2 is 10.62±0.03eV (0.37eV lower than reported by ...The vacuum ultraviolet photoionization spectrum of Si(CH3)2Cl2 has been obtained with synchrotron radiation source. The adiabatic iomzation potential of Si(CHa)2Cl2 is 10.62±0.03eV (0.37eV lower than reported by PES), and the appearance potentials for Si(CH3)Cl2, Si(CH3)2Cl+, SiCH3+ and SiCl+ are 11.25±0.03eV,12.69±0.04eV, 15. 1±0.1eV and 21.16eV±0.1eV respectively. From these results, we estimate D(Si(CH3)Cl2+-CH3)=0.631±0.03eV and D(Si(CH3)2Cl+-Cl))=2.07±0.04eV.展开更多
The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm wasstudied with synchrotron radiation source. The adiabatic ionization potentials of moleculeSi(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0....The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm wasstudied with synchrotron radiation source. The adiabatic ionization potentials of moleculeSi(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0.02 eV and 7.00±0.03 eV respectively. Inaddition, the appearance potentials of Si(CH3)2Cl+, Si(CH3)3+, SiCl+ and SiCH3+ weredetermined:AP(Si(CH3)2Cl+) ＝10.49±0.02eV, AP(Si(CH3)3+) ＝ 11.91 ±0.02eVAP(SiCl+) ＝ 18.64 ±0.06eV, AP(SiCH3+)＝ 18.62 ±0.02eVFrom these, some chemical bond energies of Si(CH3)3Cl+ were calculated:D(Si(CH3)2Cl+ - CH3) ＝0.43 ±0.02eV, D(Si(CH3)3+ - Cl) ＝ 1.85 ± 0.02eVD(SiCH3+ - (2CH3 ＋ Cl)) ＝ 8.56 ± 0．06eV, D(SiCH3+ - 2CH3) ＝6.71±0．06eVD(SiCl+ - 3CH3) ＝ 8.58 ± 0.06eV, D(SiCl＋- 2CH3) ＝ 8.15 ±0.06eVD(SiCH3+- (CH3 ＋ Cl)) ＝8.13 ±0.展开更多
The mechanisms of the CH2＋ O2→ H2O＋ CO and CH2＋ O2→ H2＋ CO2 reactions have been studied by performing ab initio CAS(8,8)/6-31G(d,p) calculations, and five intermediates(IMn) and eight transitions(TSn) have been ...The mechanisms of the CH2＋ O2→ H2O＋ CO and CH2＋ O2→ H2＋ CO2 reactions have been studied by performing ab initio CAS(8,8)/6-31G(d,p) calculations, and five intermediates(IMn) and eight transitions(TSn) have been located along the reaction paths. The predicted path for the CH2＋ O2→ H2O＋ CO is: CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS5→ H2O＋ CO. For the CH2＋ O2→ H2＋ CO2 reaction, there are two paths: (i) CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS6→ H2＋ CO2 and (ii) CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS7→ IM4b→ TS8→ H2＋ CO2, with the latter path more favorable energetically.展开更多
文摘The reaction of methylene radicals in their 3 B1 electronic ground state with molecular NO was studied. Pure CH2(X 3 B1 ) radicals were prodced by UV photolysis of ketene at 351 nm.The products were measured by Time-Resolved Fourier Transform Infrard (TR-FTIR) spectrometer. CO.OH .NH2 and HOCN or its isomer HNCO were found as primary prodcts and several possible channels of this reaction were suggested.
文摘The ultrafast processes of tetra-phenyl-porphyrin(TPP), tetra-t-butyl-phthalocyanine(BuPc) and nitro-tri-t-butyl-phthalocyanine (NtBuPc) have been inves-tigated using the femtosecond time-resolved fluorescence depletion method. A sharp peakof the fluorescence depletion with delay time has been observed both for TPP and BuPc.An ultrafast two-photon absorption process has been proposed to explain the sharp peakobserved. A long-lived fluorescence depletion has also been observed. It is causing by thestimulated-emission-pumping process produced by the intense probe laser pulses.
文摘The vacuum ultraviolet photoionization spectrum of Si(CH3)2Cl2 has been obtained with synchrotron radiation source. The adiabatic iomzation potential of Si(CHa)2Cl2 is 10.62±0.03eV (0.37eV lower than reported by PES), and the appearance potentials for Si(CH3)Cl2, Si(CH3)2Cl+, SiCH3+ and SiCl+ are 11.25±0.03eV,12.69±0.04eV, 15. 1±0.1eV and 21.16eV±0.1eV respectively. From these results, we estimate D(Si(CH3)Cl2+-CH3)=0.631±0.03eV and D(Si(CH3)2Cl+-Cl))=2.07±0.04eV.
文摘The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm wasstudied with synchrotron radiation source. The adiabatic ionization potentials of moleculeSi(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0.02 eV and 7.00±0.03 eV respectively. Inaddition, the appearance potentials of Si(CH3)2Cl+, Si(CH3)3+, SiCl+ and SiCH3+ weredetermined:AP(Si(CH3)2Cl+) ＝10.49±0.02eV, AP(Si(CH3)3+) ＝ 11.91 ±0.02eVAP(SiCl+) ＝ 18.64 ±0.06eV, AP(SiCH3+)＝ 18.62 ±0.02eVFrom these, some chemical bond energies of Si(CH3)3Cl+ were calculated:D(Si(CH3)2Cl+ - CH3) ＝0.43 ±0.02eV, D(Si(CH3)3+ - Cl) ＝ 1.85 ± 0.02eVD(SiCH3+ - (2CH3 ＋ Cl)) ＝ 8.56 ± 0．06eV, D(SiCH3+ - 2CH3) ＝6.71±0．06eVD(SiCl+ - 3CH3) ＝ 8.58 ± 0.06eV, D(SiCl＋- 2CH3) ＝ 8.15 ±0.06eVD(SiCH3+- (CH3 ＋ Cl)) ＝8.13 ±0.
文摘The mechanisms of the CH2＋ O2→ H2O＋ CO and CH2＋ O2→ H2＋ CO2 reactions have been studied by performing ab initio CAS(8,8)/6-31G(d,p) calculations, and five intermediates(IMn) and eight transitions(TSn) have been located along the reaction paths. The predicted path for the CH2＋ O2→ H2O＋ CO is: CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS5→ H2O＋ CO. For the CH2＋ O2→ H2＋ CO2 reaction, there are two paths: (i) CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS6→ H2＋ CO2 and (ii) CH2＋ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS7→ IM4b→ TS8→ H2＋ CO2, with the latter path more favorable energetically.
