Can classical marcus theory describe hole transfer in polyethylene?
Can classical marcus theory describe hole transfer in polyethylene?
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DOI：
10.1109/tdei.2016.7736861
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发表时间：
2016-10
影响因子：
3.1
通讯作者：
Masahiro Sato;A. Kumada;K. Hidaka;T. Hirano;F. Sato
中科院分区：
文献类型：
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作者：
Masahiro Sato;A. Kumada;K. Hidaka;T. Hirano;F. Sato
最近，已通过Marcus理论研究了聚乙烯（PE）低聚物中的空穴迁移率。虽然众所周知，马库斯理论成功地应用于各种有机半导体，但严格来说，有机分子中的电荷转移需要量子力学处理来解释振动能级之间的量子核隧穿。我们评估的费米的黄金法则（FGR）率表达式和经典的马库斯率表达式在不同的温度和充满活力的无序PE低聚物之间的空穴传输速率。结果表明，Marcus理论可以很好地近似描述空穴在重组能较小的聚乙烯长链之间或在高能量无序体系中的传递。然而，由Marcus理论计算的C10H22分子之间的空穴跳跃速率比通过FGR速率表达式计算的小约100倍。高温近似必须谨慎应用，特别是在PE中的空穴传输速率的定量评估。
Recently, hole mobilities in polyethylene (PE) oligomers has been investigated by means of Marcus theory. Although it is well known that Marcus theory is successfully applied to various organic semiconductors, strictly speaking, charge transfer in organic molecules requires quantum mechanical treatment to account for quantum nuclear tunneling between vibrational levels. We evaluate hole transfer rates between PE oligomers by Fermi's golden rule (FGR) rate expression and by classical Marcus rate expression at various temperature and energetic disorder. The results indicate that Marcus theory can be a good approximation for describing hole transfer between long polyethylene chain with small reorganization energy or in highly energetically disordered system. However, hole hopping rate between C10H22 molecules computed by Marcus theory was roughly 100 times smaller than that computed through FGR rate expression. High-temperature approximation must be applied with caution especially for quantitative evaluation of hole transfer rates in PE.