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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >EPR Studies on a Binitroxide Fullerene Derivative in the Ground Triplet and First Photoexcited Quintet State
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EPR Studies on a Binitroxide Fullerene Derivative in the Ground Triplet and First Photoexcited Quintet State

机译：在基态三重态和第一个光激发五重态下的二氧化氮富勒烯衍生物的EPR研究

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摘要

A fulleropyrrolidine with two covalently linked nitroxides has been studied by cw-EPR in its ground state and by TR-EPR and spin-echo detected EPR in the photoexcited state after pulsed laser excitation. The electron exchange interaction between the two unpaired electrons in the ground state is obtained from the analysis of the EPR spectra in the dark. The EPR signal of photoexcited samples consists of the superposition of the Q_((±2)) <-> Q_((±1)) and of the Q_((±1)) <-> Q_((0)) transitions of the excited quintet state and of the signal due to the triplet state of the ground state biradical. The assignment to the quintet excited state was made by measuring the frequency of the echo detected transient nutation. Fourier transformation of the transient spectra along the microwave pulse length allowed us to disentangle the quintet transitions and to obtain precise measurements of the zero-field splitting parameters. The observed polarizations in the transient spectra are examined on the basis of selective intersystem crossing due to spin-orbit interaction and quintet-singlet mixing caused by the electron dipolar interaction.
机译：在脉冲基态下，通过cw-EPR和TR-EPR研究了带有两个共价连接的一氧化氮的全吡咯烷并通过自旋回波在光激发态下检测到EPR。通过分析黑暗中的EPR光谱，可以获得基态中两个未成对电子之间的电子交换相互作用。光激发样品的EPR信号由Q _（（±2））<-> Q _（（±1））和Q _（（±1））<-> Q _（（0））跃迁的叠加组成由于基态双基态的三重态，激发五重态和信号。通过测量回波检测到的瞬态章动频率来确定五重态激发态。沿微波脉冲长度对瞬态光谱进行傅立叶变换，使我们能够解开五重音跃迁，并获得零场分裂参数的精确测量值。由于电子双极相互作用导致的自旋轨道相互作用和五重峰-单峰混合，在选择性系统间交叉的基础上检查了瞬态光谱中观察到的极化。

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