蓝的超快光化学反应动态的初步研究
Takao Kobayashi1, Motoyuki Shiga, Akinori Murakami
1Mitsubishi Chemical Group Science and Technology Research Center, Inc., 1000 Kamoshida-cho, Aoba-ku, Yokohama 227-8502, Japan. kobayashi.takao@ms.m-kagaku.co.jp
Journal of the American Chemical Society
|May 3, 2007
概括
蓝 (PB) 由于光化学反应而表现出超快的基本状态恢复. 分子动力学模拟显示了在形交叉点附近的快速S1到S0状态过渡,随后是振动连贯.
科学领域:
- 摄影化学的使用.
- 分子动力学分子动力学
- 频谱学是一种光谱学.
背景情况:
- 蓝 (PB) 是一种因其solvatochromic特性而闻名的印素染料.
- 最近的探头 (PP) 测量表明,在光刺激后的五秒钟内,PB的基态恢复超快.
研究的目的:
- 研究蓝的超快光化学反应机制.
- 阐明在探头实验中观察到的基态恢复的动态.
主要方法:
- 使用完整的活性空间自相一致场 (CASSCF) 方法进行直接的初始计算.
- 采用轨迹表面跳跃 (TSH) 技术的非adiabatic分子动力学模拟.
- 对轨迹表面跳跃事件和振动动态的分析.
主要成果:
- 模拟显示表面跳跃从激发S1状态到S0状态在S1/S0圆交叉点附近的110-120fs.
- 衰变到S0状态分为前向和反向路径,具有相似的分支比.
- 轨迹在200-300 fs达到S0最小能量区域,与实验观测相一致.
- 在S0状态下观察到低频连贯振动 (43厘米-1),归因于光激发.
结论:
- 这项研究阐明了控制蓝的基本状态恢复的超快光化学机制.
- 计算结果与实验探头数据一致,验证了拟议的机制.
- 这些发现突出了形交叉点和连贯振动在染料光动力学中的作用.
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