The effect of solvation on the conformation of acetylene has been studied by adding one water molecule at a time. Quantum chemical calculations of the n＋ （C2H2）（H2O）n （n=1-5） clusters indicate that the H2O mole...The effect of solvation on the conformation of acetylene has been studied by adding one water molecule at a time. Quantum chemical calculations of the n＋ （C2H2）（H2O）n （n=1-5） clusters indicate that the H2O molecules prefer to form the OH...Tr interaction rather than the CH...O interaction. This solvation motif is different from that of neutral （C2H2）（H2O）n （n=1-4） clusters, in which the H2O molecules prefer to form the CH...O and OH...C Hbonds. For the H＋（C2H2）（H2O）n cationic clusters, the first solvation shell consists of one ring structure with two OH...Tr H-bonds and three water molecules, which is completed at n=4. Simulated infrared spectra reveal that vibrational frequencies of OH... H-bonded O-H stretching afford a sensitive probe for exploring the solvation of acetylene by protonated water molecules. Infrared spectra of the H＋ （C2H2）（H2O）n （n=1-5） clusters could be readily measured by the infrared photodissociation technique and thus provide useful information for the understanding of solvation processes.展开更多
Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS （A C14H10 or anthracene） were generated via electrospray ionization, and characterized by magnetic-bottle photoelec- tron spectroscopy, velocity-map imagi...Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS （A C14H10 or anthracene） were generated via electrospray ionization, and characterized by magnetic-bottle photoelec- tron spectroscopy, velocity-map imaging （VMI） photoelectron spectroscopy, and quantum chemical calculations. The electron affinity （EA） and spin-orbit （SO） splitting of the APS＂ radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA （2.62-4-0.05） eV and SO splitting （43-4-7） meV. VMI photoelectron images show strong and sharp peaks near the detachment threshold with an identical electron kinetic energy （eKE） of 17.9 meV at three different detachment wavelengths, which are therefore assigned to autodetachment from dipole-bound anion states. The B3LYP/6-31＋＋G（d,p） calculations indicate APS has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.21273232 and No.21327901） and the Key Research Program of the Chinese Academy of Science （No.KGZD-EW-T05）. Ling Jiang acknowledges Hundred Talents Program of Chinese Academy of Sciences and Collaborative Innovation Center of Chemistry for Energy and Materials.
文摘The effect of solvation on the conformation of acetylene has been studied by adding one water molecule at a time. Quantum chemical calculations of the n＋ （C2H2）（H2O）n （n=1-5） clusters indicate that the H2O molecules prefer to form the OH...Tr interaction rather than the CH...O interaction. This solvation motif is different from that of neutral （C2H2）（H2O）n （n=1-4） clusters, in which the H2O molecules prefer to form the CH...O and OH...C Hbonds. For the H＋（C2H2）（H2O）n cationic clusters, the first solvation shell consists of one ring structure with two OH...Tr H-bonds and three water molecules, which is completed at n=4. Simulated infrared spectra reveal that vibrational frequencies of OH... H-bonded O-H stretching afford a sensitive probe for exploring the solvation of acetylene by protonated water molecules. Infrared spectra of the H＋ （C2H2）（H2O）n （n=1-5） clusters could be readily measured by the infrared photodissociation technique and thus provide useful information for the understanding of solvation processes.
基金supported by the U.S.Department of Energy(DOE),Office of Science,Office of Basic EnergySciences,Division of Chemical Sciences,Geosciences and Biosciences,and was performed using EMSLa national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory,which is operated by Battelle Memorial Institute for the DOEsupported by the National Science Foundation under Grant(No.CHE-1664799)
文摘Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS （A C14H10 or anthracene） were generated via electrospray ionization, and characterized by magnetic-bottle photoelec- tron spectroscopy, velocity-map imaging （VMI） photoelectron spectroscopy, and quantum chemical calculations. The electron affinity （EA） and spin-orbit （SO） splitting of the APS＂ radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA （2.62-4-0.05） eV and SO splitting （43-4-7） meV. VMI photoelectron images show strong and sharp peaks near the detachment threshold with an identical electron kinetic energy （eKE） of 17.9 meV at three different detachment wavelengths, which are therefore assigned to autodetachment from dipole-bound anion states. The B3LYP/6-31＋＋G（d,p） calculations indicate APS has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.
