...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America. >Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution
【24h】

Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution

机译：Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相关主题

摘要

We investigate the ultrafast transient absorption response of tetrakis(mu-pyrophosphito) diplatinate(II), Pt-2(mu-P2O5H2)(4)(4-) hereafter abbreviated Pt(pop), in acetonitrile upon excitation of its lowest singlet (1)A(2u) state. Compared with previously reported solvents van der Veen RM, Cannizzo A, vanMourik F, Vlcek A, Jr, CherguiM(2011) J Am Chem Soc 133:305-315, a significant shortening of the intersystem crossing (ISC) time (1 ps) from the lowest singlet to the lowest triplet state is found, allowing for a transfer of vibrational coherence, observed in the course of an ISC in a polyatomic molecule in solution. Density functional theory (DFT) quantum mechanical/molecular mechanical (QM/MM) simulations of Pt( pop) in acetonitrile and ethanol show that high-lying, mostly triplet, states are strongly mixed and shifted to lower energies due to interactions with the solvent, providing an intermediate state (or manifold of states) for the ISC. This suggests that the larger the solvation energies of the intermediate state(s), the shorter the ISC time. Because the latter is smaller than the pure dephasing time of the vibrational wave packet, coherence is conserved during the spin transition. These results underscore the crucial role of the solvent in directing pathways of intramolecular energy flow.

著录项

获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号