Photoionization and photodissociation of CH3CN were studied by a linear time of flight mass spectrometer coupled with 800 nm, 50 fs laser pulses at intensities of 6.3×1013-1.2×1014 W/cm2. The laser power dep...Photoionization and photodissociation of CH3CN were studied by a linear time of flight mass spectrometer coupled with 800 nm, 50 fs laser pulses at intensities of 6.3×1013-1.2×1014 W/cm2. The laser power dependences for principal ions CH3CN+, CH2CN+, CHCN+ and CCN+ were measured, which are consistent with the numbers of photons required to produce the ions via multiphoton ionization and dissociation. The results show that eight-photon non-resonant multiphoton ionization is the main photoionization mechanism of the parent ion CH3CN+, while the fragment ions were produced through the dissociation of the molecules in the super-excited states.展开更多
Cloud electrification is one of the oldest unresolved puzzles in the atmospheric sciences. Though many mechanisms for charge separation in clouds have been proposed, a quantitative understanding of their respective co...Cloud electrification is one of the oldest unresolved puzzles in the atmospheric sciences. Though many mechanisms for charge separation in clouds have been proposed, a quantitative understanding of their respective contribution in a given meteorological situation is lacking. Here we suggest and analyze a hitherto little discussed process. A qualitative picture at the molecular level of the charge separation mechanism of lightning in a thundercloud is proposed. It is based on two key physical/chemical natural phenomena, namely, internal charge separation of the atmospheric impurities/aerosols inside an atmospheric water cluster/droplet/ice particle and the existence of liquid water layers on rimers (graupels and hailstones) forming a layer of dipoles with H<sup>+</sup> pointing out from the air-water interface. Charge separation is achieved through strong collisions among ice particles and water droplets with the rimers in the turbulence of the thundercloud. This work would have significant contribution to cloud electrification and lightning formation.展开更多
The relaxation of the highly vibrationally excited CO (v=1-8) by CO\-2 is studied by time_resolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr\-3 with O\-...The relaxation of the highly vibrationally excited CO (v=1-8) by CO\-2 is studied by time_resolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr\-3 with O\-2 generates the highly vibrationally excited CO(v) molecules. TR FTIR records the intense infrared emission of CO(v→v-1). The vibrational populations of each level of CO(v) have been determined by the method of spectral simulation. Based on the evolution of the time resolved populations and the differential method, 8 energy transfer rate constants of CO(v=1-8) to CO 2 molecules are obtained: (5.7±0.1), (5.9±0.1), (5.2±0.2), (3.4±0.2), (2.4±0.3), (2.2±0.4), (2.0±0.4) and (1.8±0.6) (10 -14 cm 3·molecule -1·s -1), respectively. A two_channel energy transfer model can explain the feature of the quenching of CO(v) by CO 2. For the lower vibrational states of CO, the vibrational energy transfers preferentially to the υ\-3 mode of CO 2. For the higher levels, the major quenching channel changes to the vibrational energy exchange between CO(v→v-1) and the υ\-1 mode of CO 2.展开更多
The vibrational energy transfer from highly vibrationally excited CO to H 2O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of C...The vibrational energy transfer from highly vibrationally excited CO to H 2O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr 3 and O 2 the secondary reactions generate CO(v). The infrared emission of CO(v→v-1) is detected by TR FTIR. The excitation of H 2O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H 2O system are obtained: (1.7±0.1), (3.4±0.2), (6.2±0.4), (8.0±1.0), (9.0±2.0), (12±3), (16±4) and (18±7) (10 -13cm 3·molecule -1·s -1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH and ab initio calculations, the quenching mechanism of CO(v) by H 2O is suggested.展开更多
The laser pulse width effect on the dis- sociation probability of CH4+ irradiated by an ultrafast laser has been investigated experimentally and theoretically. The femtosecond laser at 800 nm with an intensity of 8.0 ...The laser pulse width effect on the dis- sociation probability of CH4+ irradiated by an ultrafast laser has been investigated experimentally and theoretically. The femtosecond laser at 800 nm with an intensity of 8.0 × 1013 W/cm2 was used. The ob- served relative yield of the primary fragment ion CH3+ increases with increasing pulse width and tends to saturate when the pulse width is longer than 120 fs. The field-assisted dissociation (FAD) model and quasi-classical trajectory (QCT) calculation were ap- plied to predicting the dissociation probability of CH4+. The calculated probability is corrected with the mo- lecular orientation effect and the spatial distribution of laser intensity. The modified results show that the dissociation requires at least 23 fs and saturates with long pulse widths (≥100 fs). The result is ap- proximately consistent with the experimental observa- tion.展开更多
文摘Photoionization and photodissociation of CH3CN were studied by a linear time of flight mass spectrometer coupled with 800 nm, 50 fs laser pulses at intensities of 6.3×1013-1.2×1014 W/cm2. The laser power dependences for principal ions CH3CN+, CH2CN+, CHCN+ and CCN+ were measured, which are consistent with the numbers of photons required to produce the ions via multiphoton ionization and dissociation. The results show that eight-photon non-resonant multiphoton ionization is the main photoionization mechanism of the parent ion CH3CN+, while the fragment ions were produced through the dissociation of the molecules in the super-excited states.
文摘Cloud electrification is one of the oldest unresolved puzzles in the atmospheric sciences. Though many mechanisms for charge separation in clouds have been proposed, a quantitative understanding of their respective contribution in a given meteorological situation is lacking. Here we suggest and analyze a hitherto little discussed process. A qualitative picture at the molecular level of the charge separation mechanism of lightning in a thundercloud is proposed. It is based on two key physical/chemical natural phenomena, namely, internal charge separation of the atmospheric impurities/aerosols inside an atmospheric water cluster/droplet/ice particle and the existence of liquid water layers on rimers (graupels and hailstones) forming a layer of dipoles with H<sup>+</sup> pointing out from the air-water interface. Charge separation is achieved through strong collisions among ice particles and water droplets with the rimers in the turbulence of the thundercloud. This work would have significant contribution to cloud electrification and lightning formation.
文摘The relaxation of the highly vibrationally excited CO (v=1-8) by CO\-2 is studied by time_resolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr\-3 with O\-2 generates the highly vibrationally excited CO(v) molecules. TR FTIR records the intense infrared emission of CO(v→v-1). The vibrational populations of each level of CO(v) have been determined by the method of spectral simulation. Based on the evolution of the time resolved populations and the differential method, 8 energy transfer rate constants of CO(v=1-8) to CO 2 molecules are obtained: (5.7±0.1), (5.9±0.1), (5.2±0.2), (3.4±0.2), (2.4±0.3), (2.2±0.4), (2.0±0.4) and (1.8±0.6) (10 -14 cm 3·molecule -1·s -1), respectively. A two_channel energy transfer model can explain the feature of the quenching of CO(v) by CO 2. For the lower vibrational states of CO, the vibrational energy transfers preferentially to the υ\-3 mode of CO 2. For the higher levels, the major quenching channel changes to the vibrational energy exchange between CO(v→v-1) and the υ\-1 mode of CO 2.
文摘The vibrational energy transfer from highly vibrationally excited CO to H 2O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr 3 and O 2 the secondary reactions generate CO(v). The infrared emission of CO(v→v-1) is detected by TR FTIR. The excitation of H 2O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H 2O system are obtained: (1.7±0.1), (3.4±0.2), (6.2±0.4), (8.0±1.0), (9.0±2.0), (12±3), (16±4) and (18±7) (10 -13cm 3·molecule -1·s -1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH and ab initio calculations, the quenching mechanism of CO(v) by H 2O is suggested.
文摘The laser pulse width effect on the dis- sociation probability of CH4+ irradiated by an ultrafast laser has been investigated experimentally and theoretically. The femtosecond laser at 800 nm with an intensity of 8.0 × 1013 W/cm2 was used. The ob- served relative yield of the primary fragment ion CH3+ increases with increasing pulse width and tends to saturate when the pulse width is longer than 120 fs. The field-assisted dissociation (FAD) model and quasi-classical trajectory (QCT) calculation were ap- plied to predicting the dissociation probability of CH4+. The calculated probability is corrected with the mo- lecular orientation effect and the spatial distribution of laser intensity. The modified results show that the dissociation requires at least 23 fs and saturates with long pulse widths (≥100 fs). The result is ap- proximately consistent with the experimental observa- tion.
