最近在第一原理的預測，在金和有共振結構之分子間，分子之Pi電子會和金屬表面電子互相共振。在本研究中，我們試圖使用表面電漿子觀察分子之Pi電子和金屬表面電子互相共振行為。我們觀察到，在玻璃基板上表面無界面活性劑金奈米粒子之表面電漿子吸收峰在638 nm。當使用自組裝方式，將表面無界面活性劑金奈米粒子黏附在玻璃基板上時，表面電漿子吸收峰分裂為615 nm和643 nm。並更進一步使用X光光電子圖譜儀(XPS)觀察其鍵結能量變化，發現金的4 f7/2軌域鍵結能量有輕微藍移的變化(~0.3 eV)，但在硫的3s軌域鍵結能量有較大紅移變化(2.8 eV)，由此察知Pi電子和金屬表面電子互相作用行為，其行為包含著使4 f7/2軌域鍵結能量藍移的共價鍵和使3s軌域鍵結能量紅移之Pi電子共振行為。並將共價鍵和Pi電子共振行為加入至古典偶和介電模型解釋表面電漿子吸收峰分裂現象。由此模型，Pi電子會參予金電子氣之震盪行為。及當金奈米粒子表面25 %之原子受到硫鍵結時，因偶和介電常數經過零點兩次，表面電漿子的吸收峰即會分裂。但當全部表面原子受到硫鍵結時，此時表面電漿子的吸收峰將因偶和介電常數只有經過零點一次而剩下一個。
在本研究中，我們亦討論表面電漿子對金奈米結構螢光閃爍效應之影響。我們使用不同尺寸海膽形狀金奈米粒子改變表面電漿子共振強度，以產生不同的電偏壓，改變螢光閃爍效應之反應活化能量。我們發現表面電漿共振產生之強電磁場可使螢光閃爍中亮的過程機會增加。更進一步，我們將螢光閃爍中亮的過程機會增加之海膽形狀金奈米粒子用於激發天然植物葉綠素之發光，並期待未來可用於生物發光激發器。

Recently, the effect of Pi-bonding electrons conjugating to the gold surface has been predicated by first principles. In this paper, we observe surface plasmon resonance splitting due to the covalence and Pi-bonding electrons conjugated effect. When surfactant-less Au NPs are linked on the glass substrate by sulfur, the SPR peak is split from one mode (638 nm) into two modes at 615 nm and 643 nm. The binding energy of 3s electrons for sulfur atoms has a huge red-shift in XPS peaks to confirm the Pi-bonding electrons conjugated effect. Furthermore, a proposed classical coupling dielectric function model, adding the gold-sulfur covalence bonding effect and conjugated Pi-bond electrons from sulfur to gold into the Drude model, is achieved to explain the mechanism of the SPR split phenomenon. In the extreme case, when the Au surface atoms are all covered by thiol sulfur atoms, or not covered at all by thiols, the SPR peak will not split.
The surface plasmon resonance (SPR) effect on the blinking emission of photoluminescence from noble metal nanostructures is still an open question in quantum mechanics and limits their applications. We investigate the emission intermittency of noble metal nanostructures by tuning the reaction potential threshold via SPR from different sized nano-sea-urchins (NSUs). (We study here sea-urchin-shaped nanoparticles which we refer to simply as "nano-sea-urchins" (NSUs).) The probability of “on” process in one photon luminescent emission intermittency of NSUs increases due to the strong electric field of SPR. The mechanism was explained by our proposed reaction potential threshold model. Furthermore, the ameliorated photoluminescence of NSU is strong enough to excite waterweed bioluminescence to act as in vivo bio light emitting device, which has potential applications in bio-imaging and bio-labeling.

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