Study on Excited State Interaction by Time-Resolved Spectroscopy

激发态相互作用的时间分辨光谱研究

• 批准号: 03453019
• 负责人: SHIBUYA Kazuhiko
• 金额: $ 0.45万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453019/
• 关键词: OODR; spin-orbit interaction; treansient absortion; photothermal spectroscopy; nitrogen dioxide; naphtalene; fullerene; benzophenone; 光一光二重共鳴; ジフェニルアミン

The visible absorption bands of NO_2 in the 588-591-nm range have been proved to contan a vibronic transition to the dark C^2A_2 state by rotational analysis using the optical-optical double-resonance (OODR) techniques. The intermediate state is verified to be a mixed state of dark C^2A_2 and light A^2B_2 coupled by spin-orbit inter- action with the selection rules DELTAN=*1 and DELTAKa=0. Although the C^2A_2 state is dark in the v_1 transition from X^2A_1, it becomes a light state in the v_2 transition to 2^2B_2.Transient absorption and time-resolved thermal lensing techniques have been used to study the photophysical behavior of C_<60> in benzene solution at room tempeature. The riplet state was the only transient species detectable with the 10 ns time- resolution. The triplet-triplet absorption spectrum with apparent band peaks at 330 and 745 nm covers the whole spectral range of 290-850 nm. The riplet lifetime in air-free benzene is 49*1 mus and essentially all the photon energy absorbed is released as heat, predominantly through the triplet state.A time-resolved thermal lensing (TRTL) technique was applied to the determina- tion of the dissociation quantum yield of benzophenone in the highly-excited triplet state yielding two phenyl radicals and a carbon monoxide. The TRTL signals were simulated using a kinetic model inculuding the S_1*S_0 and T_n*T_1 absorptions of benzophenone and subsequent dissociation of the Tn molecule. The reaction quantum yield and the heat of reaction in benzene solution were determined to be 0.36 and 126 kcal mol^<-1>, respectively, based on the experiment and simulation.

利用光学-光学双共振（OODR）技术对NO_2分子在588-591 nm的可见吸收带进行了转动分析，证实了NO_2分子在588-591 nm的可见吸收带中含有一个向暗态C^2A_2的电子振动跃迁。中间态是暗态C^2A_2和亮态A^2B_2的混合态，通过自旋-轨道相互作用耦合，选择规则为Δ N =*1和Δ Ka =0.虽然C^2A_2态在从X^2A_1到2^2B_2的v_1跃迁中是暗态，但在v_2跃迁到2^2B_2时，它变成了亮态<60>。在10 ns的时间分辨率下，Riplet态是唯一可探测到的瞬态粒子.在330和745 nm处具有明显带峰的三重态-三重态吸收光谱覆盖了290-850 nm的整个光谱范围。利用时间分辨热透镜（TRTL）技术测定了二苯甲酮在高激发三重态下的离解量子产率，得到两个苯基自由基和一氧化碳. TRTL信号用包括二苯甲酮的S_1*S_0和Tn *T_1吸附以及随后Tn分子解离的动力学模型进行了模拟。根据实验和模拟结果，确定了苯溶液中的反应量子产率和反应热分别为0.36和126 kcal mol/L<-1>。

项目成果

Y.Kajii,T.Suzuki,Y.Takatori,K.Shibuya,K.Obi: "Photodissociation of Highly-Excited Triplet State of Benzophenone Studied by a Time-Resolved Thermal Lensing Technique" Bull.Chem.Soc.Jpn.65. 1349-1355 (1992)

Y.Kajii、T.Suzuki、Y.Takatori、K.Shibuya、K.Obi：“通过时间分辨热透镜技术研究二苯甲酮高激发三重态的光解离”Bull.Chem.Soc.Jpn.65。

W. Sisk, H. Endo, K. Shibuya, K. Obi: "NO A^2SIGMA^+-X^2PI Chemiluminescence Produced from the Reaction of Excited NO_2 with Acetyleme and Its Derivatives in Their Triplet States" J. Phys. Chem.96. 6668-6674 (1992)

W. Sisk、H. Endo、K. Shibuya、K. Obi：“NO A^2SIGMA^ -X^2PI 化学发光是由激发的 NO_2 与乙酰leme 及其三重态衍生物的反应产生的” J. Phys。

Y. Kajii, K. Takeda, K. Shibuya: "Photochemical reaction of C_<60> in the presence of triethylamine in tolueme" Chem. Phys. Letters. 204. 283-286 (1993)

Y. Kajii、K. Takeda、K. Shibuya：“甲苯中三乙胺存在下 C_<60> 的光化学反应”Chem。

T.Suzuki: "Photocyclization of Diphenylamine Studied by TimeーResolved Thermal Lensing:Heat of Reactions,Energetics and Reactivety of Intermediates" Bull.Chem.Soc.Jpn.

T.Suzuki：“通过时间分辨热透镜研究二苯胺的光环化：反应热、中间体的能量和反应性”Bull.Chem.Soc.Jpn。

T.Suzuki,Y.Kajii,K.Shibuya,K.Obi: "Relaxation processes of highly excited naphthalene in solution studied by time-resolved thermal lensing technique" Chemical Physics. 161. 447-452 (1992)

T.Suzuki，Y.Kajii，K.Shibuya，K.Obi：“通过时间分辨热透镜技术研究溶液中高度激发的萘的弛豫过程”化学物理。