飞秒强激光场中液相多原子分子的振动弛豫和内转换动力学研究
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摘要
随着超快激光脉冲技术的发展，在飞秒时间尺度内研究分子的动力学行为已经成为重要的研究课题。飞秒激光脉冲技术促进了分子动力学的时间分辨光谱实验和理论研究的迅速发展。目前，利用波包理论研究飞秒时间尺度内的分子动力学现象还没有包括环境的影响，即波包动力学适合于研究气相情况。鉴于多数化学反应和几乎所有的生物化学反应是在液相体系中发生的，对液相中分子的超快动力学过程的研究成为揭示与生命过程本质密切相关的生物化学反应的重要手段，此时需要考虑诸如退相过程和振动弛豫过程等效应。在理论描述中，人们通常应用密度矩阵理论研究分子系统与环境的相互作用，其中约化密度算符、量子主方程等均可用来描述分子系统的弛豫现象。
本论文的主要内容是基于微扰密度矩阵方法和瞬态线性极化率理论研究液相多原子分子的超快动力学问题。通过自编程序，计算了多原子分子的飞秒时间分辨荧光亏蚀光谱。根据瓦维洛夫定理，荧光来自激发态的基振动能级向基电子态的跃迁，荧光强度正比于激发态的布居数，荧光亏蚀反映了激发态的弛豫动力学，因此可以利用荧光亏蚀谱探测分子动力学过程。首先，通过计算荧光亏蚀谱研究了超快振动弛豫过程和溶剂化效应，探讨了温度和探测脉冲对染料分子Rhodamine700和Oxazine750荧光亏蚀谱的影响。亏蚀谱的快速衰减过程发生在几百飞秒时间内，主要反映了激发电子态S_1的振动弛豫过程，与溶质有关；慢速衰减过程发生在皮秒时间内，主要反映溶剂化效应，与所用溶剂有关。其次，计算了叶绿素a分子在乙酸乙酯溶剂中的荧光亏蚀谱，研究了内转换过程。所计算结果与实验数据符合较好。同时还讨论了内转换对荧光亏蚀谱的影响。随着内转换时间的减少，荧光亏蚀增加。再次，计算了叶绿素a分子在二乙醚溶剂中Q_3→S_21及S_2→S_1的内转换时间。为了研究叶绿素a分子在二乙醚溶剂中从S_3态到S_1态的内转换路径，建立了一个理论模型并进行了理论计算。研究结果表明，间接内转换过程与实验结果相符。最后，利用微扰密度矩阵方法计算了Rhodamine700分子在不同溶剂中的荧光亏蚀谱和内转换速率，研究了给体数、氢键、粘度等对荧光亏蚀谱和内转换时间的影响。
With the development of the ultra-fast laser technology, molecular dynamics on the time scale of some femtoseconds is a subject of considerable interest. The advent of femtosecond optical laser technology has prompted a rapidly increasing amount of experimental and theoretical study considering the time-resolved spectroscopic investigation of ultra-fast molecular dynamics. Recently, the possible influence of environmental degrees of freedom has not been incorporated into the calculations of wave packet dynamics on investigating dynamical phenomena in molecular systems on a femtosecond time scale. Thus, the description of wave packet dynamics has been restricted to the gas phase. As almost all the biological chemical reaction take place in liquids, studying the ultra-fast dynamics of polyatomic molecules in liquids is the key to reveal the essence of the biological chemical reaction. The effects like dephasing and vibrational relaxation processes should be taken into account. In order to consider a coupling of the molecular system to a specific environment into the theoretical description one usually utilizes the density matrix formalism. The reduced density operator, the quantum master equation, etc. have been used to describe relaxational phenomena in molecular systems.
The main works in this thesis are on the ultra-fast dynamics of polyatomic molecules in liquids using the perturbative density matrix method and the transient linear susceptibility theory. The fluorescence depletion spectrum of polyatomic molecules can be calculated within the density matrix models. According to the Vavilov theory, the fluorescence is generated by the transition from the level v=0 of the first excited electronic state S_1 to the ground electronic state S_0. The fluorescence intensity is proportional to the population of the excited electronic state. The fluorescence depletion reflects the vibrational relaxation dynamics in the electronic excited state of the molecule. Molecular dynamics can be monitored by the delay time between the pump and the probe pulses.
Firstly, the fluorescence depletion spectra (FDS) are calculated to study the
ultra-fast vibrational relaxation dynamics and the solvation effect of the excited state molecules. The effects of temperature and probe pulse parameters on the FDS are also investigated. A faster decay of the FDS with a few hundreds of femtoseconds reflects the vibrational relaxation time in the S_1 state and depends on the solute molecules. A slower decay process with a picosecond time scale reflects the solvation effect and depends on the property of solvent.
Secondly, the FDS of chlorophyll-a (chl-a) in ethyl acetate are calculated and the internal conversion (IC) process is studied. The calculated FDS of chl-a agrees well with the experimental results. The IC time on the FDS is also discussed. With decreasing the IC time, the fluorescence depletion increases.
Thirdly, the IC pathways and times between S_3 and S_1 states are investigated by simulating the FDS of chl-a in ethyl ether solvent using a theoretical model developed by us. The theoretical calculation shows that sequential IC process,S_3→S_2→S_1. agrees well with the experimental results.
At last, the FDS and IC rates of the dye Rhodamine700 in methanol. ethanol and DMSO solvents are calculated using the density matrix theory. The effects of donor number, the hydrogen-bonding, the viscosity of the solvent on the FDS and IC times are also investigated.
本论文的主要内容是基于微扰密度矩阵方法和瞬态线性极化率理论研究液相多原子分子的超快动力学问题。通过自编程序，计算了多原子分子的飞秒时间分辨荧光亏蚀光谱。根据瓦维洛夫定理，荧光来自激发态的基振动能级向基电子态的跃迁，荧光强度正比于激发态的布居数，荧光亏蚀反映了激发态的弛豫动力学，因此可以利用荧光亏蚀谱探测分子动力学过程。首先，通过计算荧光亏蚀谱研究了超快振动弛豫过程和溶剂化效应，探讨了温度和探测脉冲对染料分子Rhodamine700和Oxazine750荧光亏蚀谱的影响。亏蚀谱的快速衰减过程发生在几百飞秒时间内，主要反映了激发电子态S_1的振动弛豫过程，与溶质有关；慢速衰减过程发生在皮秒时间内，主要反映溶剂化效应，与所用溶剂有关。其次，计算了叶绿素a分子在乙酸乙酯溶剂中的荧光亏蚀谱，研究了内转换过程。所计算结果与实验数据符合较好。同时还讨论了内转换对荧光亏蚀谱的影响。随着内转换时间的减少，荧光亏蚀增加。再次，计算了叶绿素a分子在二乙醚溶剂中Q_3→S_21及S_2→S_1的内转换时间。为了研究叶绿素a分子在二乙醚溶剂中从S_3态到S_1态的内转换路径，建立了一个理论模型并进行了理论计算。研究结果表明，间接内转换过程与实验结果相符。最后，利用微扰密度矩阵方法计算了Rhodamine700分子在不同溶剂中的荧光亏蚀谱和内转换速率，研究了给体数、氢键、粘度等对荧光亏蚀谱和内转换时间的影响。
With the development of the ultra-fast laser technology, molecular dynamics on the time scale of some femtoseconds is a subject of considerable interest. The advent of femtosecond optical laser technology has prompted a rapidly increasing amount of experimental and theoretical study considering the time-resolved spectroscopic investigation of ultra-fast molecular dynamics. Recently, the possible influence of environmental degrees of freedom has not been incorporated into the calculations of wave packet dynamics on investigating dynamical phenomena in molecular systems on a femtosecond time scale. Thus, the description of wave packet dynamics has been restricted to the gas phase. As almost all the biological chemical reaction take place in liquids, studying the ultra-fast dynamics of polyatomic molecules in liquids is the key to reveal the essence of the biological chemical reaction. The effects like dephasing and vibrational relaxation processes should be taken into account. In order to consider a coupling of the molecular system to a specific environment into the theoretical description one usually utilizes the density matrix formalism. The reduced density operator, the quantum master equation, etc. have been used to describe relaxational phenomena in molecular systems.
The main works in this thesis are on the ultra-fast dynamics of polyatomic molecules in liquids using the perturbative density matrix method and the transient linear susceptibility theory. The fluorescence depletion spectrum of polyatomic molecules can be calculated within the density matrix models. According to the Vavilov theory, the fluorescence is generated by the transition from the level v=0 of the first excited electronic state S_1 to the ground electronic state S_0. The fluorescence intensity is proportional to the population of the excited electronic state. The fluorescence depletion reflects the vibrational relaxation dynamics in the electronic excited state of the molecule. Molecular dynamics can be monitored by the delay time between the pump and the probe pulses.
Firstly, the fluorescence depletion spectra (FDS) are calculated to study the
ultra-fast vibrational relaxation dynamics and the solvation effect of the excited state molecules. The effects of temperature and probe pulse parameters on the FDS are also investigated. A faster decay of the FDS with a few hundreds of femtoseconds reflects the vibrational relaxation time in the S_1 state and depends on the solute molecules. A slower decay process with a picosecond time scale reflects the solvation effect and depends on the property of solvent.
Secondly, the FDS of chlorophyll-a (chl-a) in ethyl acetate are calculated and the internal conversion (IC) process is studied. The calculated FDS of chl-a agrees well with the experimental results. The IC time on the FDS is also discussed. With decreasing the IC time, the fluorescence depletion increases.
Thirdly, the IC pathways and times between S_3 and S_1 states are investigated by simulating the FDS of chl-a in ethyl ether solvent using a theoretical model developed by us. The theoretical calculation shows that sequential IC process,S_3→S_2→S_1. agrees well with the experimental results.
At last, the FDS and IC rates of the dye Rhodamine700 in methanol. ethanol and DMSO solvents are calculated using the density matrix theory. The effects of donor number, the hydrogen-bonding, the viscosity of the solvent on the FDS and IC times are also investigated.
引文
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