新型的多维飞秒时间分辨光谱技术是在传统的超快泵浦探测技术基础上引入一束额外的超短泵浦脉冲与物质发生作用，带来新的时域和频域信息可以研究分子内激发态弛豫过程和暗态的内转换演化等超快动力学过程，精确分析复杂大分子中波数差别很小的不同拉曼振动模式相干振动动力学过程。本项目拟在推导建立分子激发态的多维时域和频域信号强度变换理论模型基础上，实验上利用30fs/7mJ/1kHz及两台OPA激光器，设计搭建pump-DFWM、pump-IVS、pump-CARS多维时间分辨光谱装置，提出减少coherent spike噪声的干扰以及优化泵浦光波长至近红外区等方法提高时间分辨率和光谱分辨率，研究染料、β-胡萝卜素、番茄红素等分子内激发态间的内转换弛豫过程和相干振动动力学过程、分子内基态以及激发态电子振动波包演化过程以及视紫红质等光敏蛋白质光致异构过程中引起的分子内相干振动超快动力学过程。

Multidimensional femtosecond time-resolved spectroscopy is a novel technique based on the combination of tradition ultrafast pump-probe technique with an additional excitation pump pulse. The newly obtained intramolecular time-domain and frequency-domain spectra information could be used to analysis the population evolution between excited states and the internal conversion of dark state, as well as vibrational coherence dynamics even from the lower wavenumber Raman vibrational modes of chromophore in biomacromolecules. This project is planned to design and build pump-DFWM, pump-IVS and pump-CARS setup based on 30fs/7mJ/1kHz laser and two OPAs. By minimizing the influence of coherent spike and optimizing the wavelength of pump to NIR region, the investigation on internal conversion between excite states and vibrational coherence dynamics of dye molecules, β-carotene and lycopene, mapping of intramolecular wavepacket flow information of ground state and excited state, as well as vibrational coherence ultrafast dynamics of photo-isomerizing chromophore in photosensitive protein such as rhodopsin is achieved with high temporal and spectra resolution.