不同波長可見光雷射激發碘分子之螢光分光光譜分析

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题名:	不同波長可見光雷射激發碘分子之螢光分光光譜分析
作者:	鄭欣宜;Cheng,Hsin-I
贡献者:	化學學系
关键词:	碘分子螢光分光光譜;DF spectrum
日期:	2013-07-24
上传时间:	2013-08-22 11:39:48 (UTC+8)
出版者:	國立中央大學
摘要:	本論文研究是以不同波長可見光雷射作為激發光源，於室溫下流動式樣品槽(slow flow cell)中激發碘分子之B3Π+0,u←X1Σ+g躍遷，並取得碘分子一系列之螢光分光光譜(dispersed fluorescence spectra)。在本實驗中會搭配使用高靈敏度增強式電荷偶合偵測器以及光電倍增管來取得碘分子激發後的螢光分光光譜與碘分子之放射生命期。我們發現先前研究關於碘分子振動能階的參數在振動量子數大時無法吻合我們的實驗數據。因此我們進行詳盡的碘分子光譜分析，涵蓋了509 nm到641 nm的九個不同波長激發的螢光分光光譜，以一個全譜帶分析(global least-squares fit)包含385個放射譜帶，振動能階含B3Π+0,u state振動量子數(v′)至54，X1Σ+g state振動量子數(v?)至45，決定了更精確的非簡諧振盪參數(anharmonicity parameters)。此外，由碘分子之放射生命期的觀測，可知碘化烷類與碘分子的共存會促使碘分子之放射生命期的縮短，這解釋了先前觀測到光解碘甲烷類分子中碘分子的放射生命期。而由532 nm雷射激發碘分子放射光譜與光解碘化烷類之未知譜帶有相當吻合之頻率，故可藉由碘分子螢光分光光譜協助未知譜帶的釐清。 Laser-induced dispersed fluorescence(DF) spectra of the I2 B3Π+0,u←X1Σ+g transition at various wavelengths were obtained in a slow flow cell at ambient temperature. A high sensitivity intensified charge-coupled device (ICCD) and a photomultiplier tube (PMT) were adopted as detectors for recording emission spectra and waveforms. Vibrational parameters of the I2 B3Π+0,u?X1Σ+g transition from previous studies were found to profoundly deviate from our data at high vibrational quantum numbers. We have therefore analyzed the DF spectra at 9 different excitation wavelengths covering the 509 nm to 641 nm region. A global least-squares fit, based on a total of 385 observed emission bands with the B3Π+0,u state vibrational quantum number (v′) up to 54 and the X1Σ+g state vibrational quantum number (v?) up to 45, was conducted to determine more accurate anharmonicity parameters. In addition, we have found the addition of CH2I2 could significantly quench the emission lifetime of the I2 B state, which is consistent with previous observations. The I2 DF spectrum excited at 532 nm is very similar to the unknown bands found in the photolysis of iodomethanes. Our analysis could also clarify the spectroscopic structure of these unknown bands.
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