A model hamiltonian tuned toward high level ab initio calculations to describe the character of excitonic states in perylenebisimide aggregates
A model hamiltonian tuned toward high level ab initio calculations to describe the character of excitonic states in perylenebisimide aggregates
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针对高水平从头算计算的哈密顿模型，用于描述苝双酰亚胺聚集体中激子态的特征
DOI：
10.1002/jcc.25374
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发表时间：
2018-09
影响因子：
3
通讯作者：
Reinhold F Fink
中科院分区：
文献类型：
--
作者：
Wenlan Liu;Sofia Canola;Andreas Köhn;Bernd Engels;Fabrizia Negri;Reinhold F Fink
以两个二苯二亚胺(PBI)分子的聚集体为例，研究了分子间排列对最低激发态电荷转移(CT)和Frenkel激子(FE)组态的影响。基于前线轨道顺(FOCIS)水平上的两个FE和两个CT组态的最小模型哈密顿量被证明是一种简单和可理解的方法，提供了对模型哈密顿矩阵元的物理意义的洞察。最近引入的分析和脱脂过程(Liu等人，J.Chem.太棒了。084106)方法提取组态能量和相互作用能量(模型哈密顿参数)也是从精确的CC2方法中得到的。根据非绝热能量分布及其相互作用的分析表明，焦点参数定性地正确地描述了绝热激发态能量分布。然而，与CC2的比较表明，在焦点水平上存在避免的交叉，与作为聚集结构的函数的激发态的大的特征变化(CT/FE)相关，这代表了焦点结果的主要缺点。结果表明，适当修正焦距衍生参数可以准确地表示作为聚集体结构函数的激发二聚态的势能面和交叉。
On the example of an aggregate of two perylenebisimide (PBI) molecules the character of the lowest excited electronic states in terms of charge transfer (CT) and Frenkel exciton (FE) configurations is investigated as a function of the intermolecular arrangement. A minimal model Hamiltonian based on two FE and two CT configurations at the frontier-orbitals CIS (FOCIS) level is shown to represent a simple and comprehensible approach providing insight into the physical significance of the model Hamiltonian matrix elements. The recently introduced analysis and diabatization procedure (Liu et al., J. Chem. Phys. 2015, 143, 084106 ) method is used to extract the energies of the configurations and their interactions (the model Hamiltonian parameters) also from the accurate CC2 approach. An analysis in terms of diabatic energy profiles and their interactions shows that the FOCIS parameters give a qualitatively correct description of the adiabatic excited state energy profiles. Comparison with CC2 reveals, however, the presence of avoided crossings at FOCIS level, associated with a large character change (CT/FE) of the excited states as a function of the aggregate structure, which represents the major drawback of FOCIS results. We show that proper amendment of the FOCIS-derived parameters allows to accurately represent the potential energy surfaces and crossings of the excited dimer states as a function of the aggregate structure.
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影响因子：
3
作者：
Wenlan Liu;Volker Settels;P. Harbach;A. Dreuw;R. Fink;B. Engels
通讯作者：
Wenlan Liu;Volker Settels;P. Harbach;A. Dreuw;R. Fink;B. Engels
影响因子：
3.7
作者：
Jing Li;G. D’Avino;I. Duchemin;D. Beljonne;X. Blase
通讯作者：
Jing Li;G. D’Avino;I. Duchemin;D. Beljonne;X. Blase
确定超快弛豫过程是苝基有机半导体中激子扩散效率低下的主要原因
影响因子：
15
作者：
V. Settels;A. Schubert;M. Tafipolski;W. L. Liu;V. Stehr;A. K. Topczak;J. Pflaum;C. Deibel;R. F. Fink;V. Engel;B. Engels
通讯作者：
B. Engels
影响因子：
2.3
作者：
R. Scholz;M. Schreiber
通讯作者：
R. Scholz;M. Schreiber
DOI：
10.1063/5.0026873
发表时间：
2020-09
期刊：
The Journal of chemical physics
影响因子：
--
作者：
D. Reichman;Xiaoyang Zhu
通讯作者：
D. Reichman;Xiaoyang Zhu