An experiment facility has been set up for the study of metal cluster compounds in our laboratory, which consists of a nano-electrospray ionization source, an ion transmission and focus system, and a reflectron time-o...An experiment facility has been set up for the study of metal cluster compounds in our laboratory, which consists of a nano-electrospray ionization source, an ion transmission and focus system, and a reflectron time-of-fight mass spectrometer. Taking advantage of the nano-electrospray ionization source, polyvalent ions are usually produced in the ＂ionization＂ process and the obtained mass resolution of the equipment is over 8000. The molecular ion peaks of metal cluster compounds [Au20（PPhpy2）10Cl2]（SbF6）4, where PPhpy2=bis（2- pyridyl）phenylphosphine, and [AuaAg2（C）L6]（BF4）4, where L=2-（diphenylphosphino）-5- methylpyridine, are distinguished in the respective mass spectrum, accompanied by some fragment ion peaks. In addition, the mass-to-charge ratios of the parent ions are determi- nated. Preliminary results suggest that the device is a powerful tool for the study of metal cluster compounds. It turns out that the information obtained by the instrumentation serves as an essential supplement to single crystal X-ray diffraction for structure characterization of metal cluster compounds.展开更多
We introduce a modification of reflectron time-of-flight mass spectrometer for laser photodissociation of mass-selected ions. In our apparatus, the ions of interests were selected by a mass gate near the first space f...We introduce a modification of reflectron time-of-flight mass spectrometer for laser photodissociation of mass-selected ions. In our apparatus, the ions of interests were selected by a mass gate near the first space focus point and decelerated right after the mass gate, were then crossed by a laser beam for dissociation. The daughter ions and surviving parent ions were re-accelerated and analyzed by the reflectron time-of-flight mass spectrometer. Compared to the designs reported by other research groups, our selection-deceleration-dissociation-reacceleration approach has better daughter-parent-ions-separation, easier laser timing, and better overlapping between the ion beam and laser beam. We also conducted detailed cal- culations on the parent ion and daughter ion flight times, and provided a simplified formula for the calibration of daughter ion mass.展开更多
Vacuum ultraviolet(VUV)photoionization and photodissociation of methylcyclohexane have been studied utilizing a reflectron time-of-flight mass spectrometer(RTOF-MS)with synchrotron radiation source.Photoionization eff...Vacuum ultraviolet(VUV)photoionization and photodissociation of methylcyclohexane have been studied utilizing a reflectron time-of-flight mass spectrometer(RTOF-MS)with synchrotron radiation source.Photoionization efficiency curves(PIEs)of molecule ion C7H14^+ and fragment ions C7H13^+,C6H11^+,C6H10+,C5H10^+,C5H9^+,C4H8^+,C4H7^+,and C3H5^+ were observed.The ionization energy of methylcyclohexane was measured to be(9.80±0.03)eV,and appearance energies of fragment ions were determined from the PIEs.Optimized structures of transitional states,intermediates and product ions were characterized at the B3LYP/6-31G(d)level and the energies were calculated using G3B3 method.Formation channels of dominating fragment ions were proposed.Intramolecular hydrogen migrations and carbon ring-opening were the foremost processes in fragmentation pathways of methylcyclohexane.展开更多
Two variants of application of a transaxial mirror with stigmatic spatial time-of-flight focusing in the time-of-flight mass spectrometer have been considered. In the first variant, the transaxial mirror is used as an...Two variants of application of a transaxial mirror with stigmatic spatial time-of-flight focusing in the time-of-flight mass spectrometer have been considered. In the first variant, the transaxial mirror is used as an ion reflector in the ordinary scheme of the time-of-flight mass reflectron. In the second variant, the transaxial mirror simultaneously fulfills the function of the ion reflector and corrector of aberrations caused by the energy spread of ions in the package, formed by the ion source of the mass reflectron. The expressions defining the conditions of stigmatic spatial time-of-flight focusing in the transaxial mirror and the combined system consisting of an ion source and a mirror have been derived. The relationships between geometrical and electrical parameters of three- and four-electrode transaxial mirrors realizing these conditions have been obtained by numerical calculations.展开更多
文摘An experiment facility has been set up for the study of metal cluster compounds in our laboratory, which consists of a nano-electrospray ionization source, an ion transmission and focus system, and a reflectron time-of-fight mass spectrometer. Taking advantage of the nano-electrospray ionization source, polyvalent ions are usually produced in the ＂ionization＂ process and the obtained mass resolution of the equipment is over 8000. The molecular ion peaks of metal cluster compounds [Au20（PPhpy2）10Cl2]（SbF6）4, where PPhpy2=bis（2- pyridyl）phenylphosphine, and [AuaAg2（C）L6]（BF4）4, where L=2-（diphenylphosphino）-5- methylpyridine, are distinguished in the respective mass spectrum, accompanied by some fragment ion peaks. In addition, the mass-to-charge ratios of the parent ions are determi- nated. Preliminary results suggest that the device is a powerful tool for the study of metal cluster compounds. It turns out that the information obtained by the instrumentation serves as an essential supplement to single crystal X-ray diffraction for structure characterization of metal cluster compounds.
基金V. ACKNOWLEDGMENTS This work supported by the National Natural Science Foundation of China （No.20853001）. We thank Professor Qi-he Zhu and Professor Zhen Gao for valuable discussions.
文摘We introduce a modification of reflectron time-of-flight mass spectrometer for laser photodissociation of mass-selected ions. In our apparatus, the ions of interests were selected by a mass gate near the first space focus point and decelerated right after the mass gate, were then crossed by a laser beam for dissociation. The daughter ions and surviving parent ions were re-accelerated and analyzed by the reflectron time-of-flight mass spectrometer. Compared to the designs reported by other research groups, our selection-deceleration-dissociation-reacceleration approach has better daughter-parent-ions-separation, easier laser timing, and better overlapping between the ion beam and laser beam. We also conducted detailed cal- culations on the parent ion and daughter ion flight times, and provided a simplified formula for the calibration of daughter ion mass.
基金supported by the National Natural Science Foundation of China(No.91544105,No.41275127,No.U1532137 and No.11575178)。
文摘Vacuum ultraviolet(VUV)photoionization and photodissociation of methylcyclohexane have been studied utilizing a reflectron time-of-flight mass spectrometer(RTOF-MS)with synchrotron radiation source.Photoionization efficiency curves(PIEs)of molecule ion C7H14^+ and fragment ions C7H13^+,C6H11^+,C6H10+,C5H10^+,C5H9^+,C4H8^+,C4H7^+,and C3H5^+ were observed.The ionization energy of methylcyclohexane was measured to be(9.80±0.03)eV,and appearance energies of fragment ions were determined from the PIEs.Optimized structures of transitional states,intermediates and product ions were characterized at the B3LYP/6-31G(d)level and the energies were calculated using G3B3 method.Formation channels of dominating fragment ions were proposed.Intramolecular hydrogen migrations and carbon ring-opening were the foremost processes in fragmentation pathways of methylcyclohexane.
文摘Two variants of application of a transaxial mirror with stigmatic spatial time-of-flight focusing in the time-of-flight mass spectrometer have been considered. In the first variant, the transaxial mirror is used as an ion reflector in the ordinary scheme of the time-of-flight mass reflectron. In the second variant, the transaxial mirror simultaneously fulfills the function of the ion reflector and corrector of aberrations caused by the energy spread of ions in the package, formed by the ion source of the mass reflectron. The expressions defining the conditions of stigmatic spatial time-of-flight focusing in the transaxial mirror and the combined system consisting of an ion source and a mirror have been derived. The relationships between geometrical and electrical parameters of three- and four-electrode transaxial mirrors realizing these conditions have been obtained by numerical calculations.
