The ionization-dissociation of methyl iodide in intense laser field has been studied using a reflection time-of-flight mass spectrometry (RTOF-MS), at a laser intensity of < or =6.6x10(14) W/cm(2), lambda=798 nm, and a pulse width of 180 fs. With the high resolution of RTOF-MS, the fragment ions with the same M/z but from different dissociation channels are resolved in the mass spectra, and the kinetic energy releases (KERs) of the fragment ions such as I(q+) (q=1-6), CH(m) (+) (m=0-3), C(2+), and C(3+) are measured. It is found that the KERs of the fragment ions are independent of the laser intensity. The fragments CH(3) (+) and I(+) with very low KERs (<1 eV for CH(3) (+) and <0.07 eV for I(+)) are assigned to be produced by the multiphoton dissociation of CH(3)I(+). For the fragments CH(3) (+) and I(+) from CH(3)I(2+), they are produced by the Coulomb explosion of CH(3)I(2+) with the interaction from the covalent force of the remaining valence electrons. The split of the KER of the fragments produced from CH(3)I(2+) dissociation is observed experimentally and explained with the energy split of I(+)((3)P(2)) and I(+)((3)P(0,1)). The dissociation CH(3)I(3+)-->CH(3) (+)+I(2+) is caused by Coulomb explosion. The valid charge distance R(c) between I(2+) and CH(3) (+), at which enhanced ionization of methyl iodide occurs, is obtained to be 3.7 A by the measurements of the KERs of the fragments CH(3) (+) and I(2+). For the CH(3)I(n+) (n> or =3), the KERs of the fragment ions CH(3) (p+) and I(q+) are attributed to the Coulomb repulsion between CH(3) (p+) and I(q+) from R(c) approximately 3.7 A. The dissociation of the fragment CH(3) (+) is also discussed. By the enhanced ionization mechanism and using the measured KER of I(q+), all the possible Coulomb explosion channels are identified. By comparing the abundance of fragment ions in mass spectrum, it is found that the asymmetric dissociation channels with more charges on iodine, q>p, are the dominant channels.
China has increased its vegetation coverage and enhanced its terrestrial carbon sink through ecological restoration since the end of the 20th century. However, the temporal variation in vegetation carbon sequestration remains unclear, and the relative effects of climate change and ecological restoration efforts are under debate. By integrating remote sensing and machine learning with a modelling approach, we explored the biological and physical pathways by which both climate change and human activities (e.g., ecological restoration, cropland expansion, and urbanization) have altered Chinese terrestrial ecosystem structures and functions, including vegetation cover, surface heat fluxes, water flux, and vegetation carbon sequestration (defined by gross and net primary production, GPP and NPP). Our study indicated that during 2001–2018, GPP in China increased significantly at a rate of 49.1–53.1 TgC/yr2, and the climatic and anthropogenic contributions to GPP gains were comparable (48%–56% and 44%–52%, respectively). Spatially, afforestation was the dominant mechanism behind forest cover expansions in the farming‐pastoral ecotone in northern China, on the Loess Plateau and in the southwest karst region, whereas climate change promoted vegetation cover in most parts of southeastern China. At the same time, the increasing trend in NPP (22.4–24.9 TgC/yr2) during 2001–2018 was highly attributed to human activities (71%–81%), particularly in southern, eastern, and northeastern China. Both GPP and NPP showed accelerated increases after 2010 because the anthropogenic NPP gains during 2001–2010 were generally offset by the climate‐induced NPP losses in southern China. However, after 2010, the climatic influence reversed, thus highlighting the vegetation carbon sequestration that occurs with ecological restoration.
The phenyl-lead metal complexes ([Pb(m)C6H5]-) produced from the reactions between benzene and lead clusters formed by laser ablation on a lead solid sample are studied by photoelectron spectroscopy (PES) and density functional theory (DFT). The adiabatic electron affinities (EAs) of [Pb(m)C6H5]- are obtained from PES at 308 nm, and the differences between the PES of [Pb(m)C6H5]- and the PES of Pbm- are discussed in detail. The results reveal that the phenyl group binds perpendicularly on lead clusters through the Pb-C sigma bond and the complexes have a closed shell structure. Calculations with DFT are carried out on the structural and electronic properties of [Pb(m)C6H5]-, and the adiabatic detachment energy for the optimized structures of anion are in agreement with the experimental PES results. The density of states (DOS) calculated is compared with experimental PES and is discussed. The most possible structures for each species are concluded, and the bonding between Pb and phenyl is analyzed, which also proves that the phenyl group binds perpendicularly on lead clusters through the Pb-C sigma bond.
By using laser ablation on mixtures of transition metal cobalt and group-14 elements, binary alloy cluster anions were produced while no binary alloy cluster cations were detected, and the homocluster cations of group-14 elements appeared at very low abundance. The differences between clustering abilities of germanium, tin and lead with cobalt are described, and the chemical bonds in the binary alloy cluster anions appear to indicate a transition from covalent to metal bonds. The cluster anion [CoPb10](-) appears in very high abundance (magic number), and an endohedral structure is proposed for this cluster. The cluster anion [CoPb12](-), also representing a magic number, probably has an icosahedral structure. Compared with solid-state Co/Ge binary alloys, the compositions of most binary alloy cluster anions are germanium-rich, in which the covalent bonds are predominant.
Iron–sulfur cluster ions FenSm+ (n=1–13, m=1–13) were produced by direct laser ablation on a solid sample containing a mixture of iron and sulfur powder. UV photodissociation of the cluster ions was studied with a tandem time-of-flight mass spectrometer. It was found that all the cluster ions with compositions of m=n, m=n−1, or m=n+5 were relatively more abundant, indicating that they were stable. The photodissociation results of the FenSm+ ions showed that, for parent ions with n≪m, the main channels were sequential losses of neutral S atoms until n∼m, while for parent ions with n∼m, the main product ions had compositions of smaller m=n or m=n−1. From these experimental results, it is proposed that the FenSn+ cluster ions might have structures similar to those of the FenS*n cores in iron–sulfur proteins, while the FenSm+ (m≳n) cluster ions could be considered to have structures with the FenSn+ cores surrounded by some peripheral S atoms.
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