曾文碧Tzeng, Wen-Bih駱可薇Lo, Ko-Wei2019-09-042013-6-142019-09-042013http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN060042022S%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/100346利用共振雙光子游離與質量解析臨界游離光譜術來探討3-氯- 4氟苯胺(3C4FA)的第一電子激發態與離子基態光譜。在目前儀器的解析極限，3-氯-4-氟苯胺同位素分子(isotopologues)具有相同的躍遷能量與絕熱游離能。我們精確的量測第一電子躍遷能和游離能分別為32 348 ± 2 cm-1 和 63 872 ± 5 cm-1。光譜分析結果顯示大部分明顯之譜峰涉及苯環的平面運動和取代基的彎曲運動。 藉由所得的數據和本實驗室先前所發表其他苯胺衍生物(鄰-氯苯胺、對-氟苯胺和苯胺)的數據做比較，可發現此分子遵循添加規則(additivity rule)以利我們預測第一電子躍遷能和游離能。為了標定光譜並且提供合理的解釋數據，我們同時也進行量子化學及密度泛函數理論計算。  We applied the resonant two-photon ionization and mass-analyzed threshold ionization spectroscopic techniques to record the vibronic and cation spectra of 3-chloro-4-fluoroaniline (3C4FA). Within our experimental detection limit, the measured values are the same for both of the 35Cl and 37Cl isotopologues of 3C4FA. The band origin of the S1 ← S0 electronic transition (E1) was found to be 32 348 ± 2 cm-1, and the adiabatic ionization energy (IE) was determined to be 63 872 ± 5 cm-1. Most of the observed active modes of 3C4FA in the electronically excited S1 and cationic ground D0 states mainly involve the in-plane ring deformation and substituent-sensitive bending vibrations. Comparing the E1‘s and IEs of 3C4FA, 3-chloroaniline, 4-fluoroaniline, and aniline, we found an additivity rule which implies weak interactions among the Cl, F, and NH2 substituents. We also performed the quantum chemical and density functional theory calculations to assign spectral bands and to provide reasonable interpretation for our experimental findings.3-氯-4-氟苯胺共振雙光子游離離子態振動光譜臨界游離第一電子激發態振動光譜3-Chloro-4-fluoroanilineResonant two-photon ionizationCation spectrumThreshold ionizationVibronic spectroscopy