Based on the mechanism analysis of the polychlorination of long chain n-alkanes by photo-initiation,a kinetic model was developed. The model parameters were obtained by the method of non-linear fitting. The influences...Based on the mechanism analysis of the polychlorination of long chain n-alkanes by photo-initiation,a kinetic model was developed. The model parameters were obtained by the method of non-linear fitting. The influences of luminous intensity and concentration of molecular chlorine on the rate of polychlorination are demonstrated by the model. If the luminous intensity is adequate, the polychlorination rate of n-alkane is only controlled by the flow rate of molecular chlorine in a wide range of temperature, and the changes of temperature and luminous intensity have less effect on the reaction rate. In addition, the predictions of chlorine content of polychlorinated n-alkane calculated with the model agree very well with experimental results.展开更多
Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level,but it has been proven to be a grand challenge for neutral clusters because the ab...Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level,but it has been proven to be a grand challenge for neutral clusters because the absence of a charge makes it di伍cult for the size selection and detection.Infrared(IR)spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser(VUV-FEL)has recently been developed in the lab.The IR-VUV depletion and IR+VUV enhancement spectroscopic techniques open new avenues for size-selected IR spectroscopies of a large variety of neutral clusters without confinement(i.e.,an ultraviolet chromophore,a messenger tag,or a host matrix).The spectroscopic principles have been demonstrated by investigations of some neutral water clusters and some metal carbonyls.Here,the spectroscopic principles and their applications for neutral clusters are reviewed.展开更多
The product channels and mechanisms of the C2HC12＋O2 reaction are investigated by step-scan time-resolved Fourier transform infrared emission spectroscopy and the G3MP2// B3LYP/6-311G（d,p） level of electronic struc...The product channels and mechanisms of the C2HC12＋O2 reaction are investigated by step-scan time-resolved Fourier transform infrared emission spectroscopy and the G3MP2// B3LYP/6-311G（d,p） level of electronic structure calculations. Vibrationally excited products of HCI, CO, and CO2 are observed in the IR emission spectra and the product vibrational state distribution are determined which shows that HCI and CO are vibrationally excited with the nascent average vibrational energy estimated to be 59.8 and 51.8 kJ/mol respectively. In combination with the G3MP2//B3LYP/6-311G（d,p） calculations, the reaction mechanisms have been characterized and the energetically favorable reaction pathways have been suggested.展开更多
文摘Based on the mechanism analysis of the polychlorination of long chain n-alkanes by photo-initiation,a kinetic model was developed. The model parameters were obtained by the method of non-linear fitting. The influences of luminous intensity and concentration of molecular chlorine on the rate of polychlorination are demonstrated by the model. If the luminous intensity is adequate, the polychlorination rate of n-alkane is only controlled by the flow rate of molecular chlorine in a wide range of temperature, and the changes of temperature and luminous intensity have less effect on the reaction rate. In addition, the predictions of chlorine content of polychlorinated n-alkane calculated with the model agree very well with experimental results.
基金This work was supported by the National Natural Science Foundation of China(No.92061203 and No.21688102)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)+3 种基金International Partnership Program of Chinese Academy of Sciences(121421KYSB20170012)Chinese Academy of Sciences(GJJSTD20190002)K.C.Wong Education Foundation(GJTD-2018-06)Dalian Institute of Chemical Physics(DICP DCLS201702).
文摘Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level,but it has been proven to be a grand challenge for neutral clusters because the absence of a charge makes it di伍cult for the size selection and detection.Infrared(IR)spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser(VUV-FEL)has recently been developed in the lab.The IR-VUV depletion and IR+VUV enhancement spectroscopic techniques open new avenues for size-selected IR spectroscopies of a large variety of neutral clusters without confinement(i.e.,an ultraviolet chromophore,a messenger tag,or a host matrix).The spectroscopic principles have been demonstrated by investigations of some neutral water clusters and some metal carbonyls.Here,the spectroscopic principles and their applications for neutral clusters are reviewed.
基金V. ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20733005, No.20673126, and No.20973179）, the National Basic Research Program of China （No.2007CB815200 and No.2007AA02Z116）, and the Chinese Academy of Sciences.
文摘The product channels and mechanisms of the C2HC12＋O2 reaction are investigated by step-scan time-resolved Fourier transform infrared emission spectroscopy and the G3MP2// B3LYP/6-311G（d,p） level of electronic structure calculations. Vibrationally excited products of HCI, CO, and CO2 are observed in the IR emission spectra and the product vibrational state distribution are determined which shows that HCI and CO are vibrationally excited with the nascent average vibrational energy estimated to be 59.8 and 51.8 kJ/mol respectively. In combination with the G3MP2//B3LYP/6-311G（d,p） calculations, the reaction mechanisms have been characterized and the energetically favorable reaction pathways have been suggested.
