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利用飛秒瞬態吸收光譜技術研究鍵結於金奈米粒子表面上的2-苯硫醇基,5-苯基,3-丁基呋喃之光學特性及三核鎳系、鈷系與鉻系金屬串錯合物之電子激發態動態學
Dissertation

利用飛秒瞬態吸收光譜技術研究鍵結於金奈米粒子表面上的2-苯硫醇基,5-苯基,3-丁基呋喃之光學特性及三核鎳系、鈷系與鉻系金屬串錯合物之電子激發態動態學

鄭照翰
Doctor of Philosophy (PHD), 國立清華大學, 化學系
2008

Abstract

超快 奈米金 電子轉移 金屬串錯合物 激發態動態學 ultrafast gold nanoparticle electron transfer metal string excited-state dynamics
Dye molecule 3SAH, gold nanoparticle (GNP), and 3SAH-GNP were measured by sub-picosecond transient absorption spectroscopy. The aggregation of 3SAH exists with concentrations larger than 1×10-6 M, and shows long emission lifetime due to more rigid structure. For 5 nm GNP, time constants of electron-phonon and phonon-phonon are obtained to be 2.3 and 140 ps, respectively in fitting to a two-temperature model. The dephasing time less than 60 fs indicates an ultrafast electron scattering. For 3SAH-GNP, the absorption of 3SAH+ arises less than 200 fs indicating the electron injection from excited 3SAH to GNP with high efficiency. The process of back electron transfer from GNP to 3SAH competes well with electron-phonon interaction in GNP, and becomes dominant under condition of large ratio of surface to volume in GNP. The participation of back electron transfer plays a second pathway for heat dissipation in GNP. Trinucleus metal complexes, Ni3(dpa)4(NCS)2, Ni3(dpa)4Cl2, Co3(dpa)4(NCS)2,and Cr3(dpa)4Cl2 are studied by transient absorption spectroscopy. Their ligand-center π-π* and charge transfer states are accessed via laser excitation then quickly transfer to ligand-field states at time constants 0.2-0.4 (Ni3), <0.1 (Co3), and <0.1 ps (Cr3), respectively. Time constants obtained for ligand-field states back to ground state are related to the spin-orbit coupling constants (Ni3 > Co3 > Cr3) and the energy gap between lowest-lying excited state and ground state (Cr3 > Co3 ≈ Ni3). They are obtained to be 3 (Ni3), 15 (Co3), and 200 ps (Cr3).

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