We have obtained the high-resolution threshold photoelectron （TPE） spectra of chlorobenzene C6HaCl （X1A1）, propargyl radical C3H3 （X2B1）, and allyl radical C3H5 （X2A1） by employing the vacuum ultraviolet （VUV...We have obtained the high-resolution threshold photoelectron （TPE） spectra of chlorobenzene C6HaCl （X1A1）, propargyl radical C3H3 （X2B1）, and allyl radical C3H5 （X2A1） by employing the vacuum ultraviolet （VUV） laser velocity-map-imaging-TPE （VUV-VMI-TPE） method. The photoelectron energy resolution of 1-2 cm^-1 observed for the VUV-VMI-TPE method is comparable to that achieved in VUV laser pulsed-field ionization-photoelectron （VUV-PFI-PE） measurements. Similar to VUV-PFI-PE measurements, the energy resolutions for VUV-VMI-photoelectron （VUV-VMI-PE） and VUV-VMI-TPE measurements are found to depend on the dc electric field F in V/cm used at the photoionization region for electron extraction. The decrease of the ionization thresholds of C6H5Cl and C3H3 observed as a function of F shows that the Stark shift correction for VUV-VMI-TPE measurements is governed by the formula -3.1√F in cm^-1, which is half of the classical prediction of -6.1v/F in cm^-1. We have also measured the VUV-VMI-PE spectra of C6H5Cl and C3H5 at VUV energies near their ionization thresholds. The cationic vibrational bands observed in the VUV-VMI-PE measurements were assigned to be the vibrational progression, nv7＋ （n=0-3）, for C3H＋. The higher experimental sensitivity and similar energy resolutions achieved in VUV-VMI-TPE compared to VUV-PFI-PE measurements make the VUV-VMI- TPE method an excellent alternative for high-resolution VUV-PFI-PE measurements.展开更多
基金This work was supported by the National Science Foundation under CHE-0910488 and CHE-1462172. C. Y. Ng also acknowledges the support by the Chemi- cal Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, （US） Department of Energy （DOE） under Contract No.DEFG02-02ER15306.
文摘We have obtained the high-resolution threshold photoelectron （TPE） spectra of chlorobenzene C6HaCl （X1A1）, propargyl radical C3H3 （X2B1）, and allyl radical C3H5 （X2A1） by employing the vacuum ultraviolet （VUV） laser velocity-map-imaging-TPE （VUV-VMI-TPE） method. The photoelectron energy resolution of 1-2 cm^-1 observed for the VUV-VMI-TPE method is comparable to that achieved in VUV laser pulsed-field ionization-photoelectron （VUV-PFI-PE） measurements. Similar to VUV-PFI-PE measurements, the energy resolutions for VUV-VMI-photoelectron （VUV-VMI-PE） and VUV-VMI-TPE measurements are found to depend on the dc electric field F in V/cm used at the photoionization region for electron extraction. The decrease of the ionization thresholds of C6H5Cl and C3H3 observed as a function of F shows that the Stark shift correction for VUV-VMI-TPE measurements is governed by the formula -3.1√F in cm^-1, which is half of the classical prediction of -6.1v/F in cm^-1. We have also measured the VUV-VMI-PE spectra of C6H5Cl and C3H5 at VUV energies near their ionization thresholds. The cationic vibrational bands observed in the VUV-VMI-PE measurements were assigned to be the vibrational progression, nv7＋ （n=0-3）, for C3H＋. The higher experimental sensitivity and similar energy resolutions achieved in VUV-VMI-TPE compared to VUV-PFI-PE measurements make the VUV-VMI- TPE method an excellent alternative for high-resolution VUV-PFI-PE measurements.
