Electronically excited states in poly(p-phenylenevinylene): vertical excitations and torsional potentials from high-level ab initio calculations.
Electronically excited states in poly(p-phenylenevinylene): vertical excitations and torsional potentials from high-level ab initio calculations.
复制标题
DOI：
10.1021/jp400372t
复制
发表时间：
2013-03-14
影响因子：
2.9
通讯作者：
Lischka, Hans
中科院分区：
文献类型：
--
作者：
Panda, Aditya N.;Plasse, Felix;Aquino, Adelia J. A.;Burghardt, Irene;Lischka, Hans
使用恒等分辨率 (RI) 方法的从头算二阶代数图解构造 (ADC(2)) 计算已在链长最多为 8 个苯环的聚（对亚苯基亚乙烯基）(PPV) 低聚物上进行。报告了四种最低 π-π* 激发的垂直激发能和最低激发态 (S1) 的几何弛豫效应。外推至无限链长表明与实验得出的类似数据具有良好的一致性。基于优化的 S1 几何结构的键长交替 (BLA) 分析为低聚物链中心缺陷的定位提供了确凿的证据。已经计算了所研究的四种激发态的扭转势，并且划分为碎片贡献的跃迁密度已用于识别激子相互作用。本研究提供了基准结果，可用于（i）作为较低水平方法的参考，以及（ii）为 PPV 型系统中超快激子传递动力学的量子动力学模拟提供有效的弗兰克尔激子哈密顿量参数化的可能性。
Ab initio second-order algebraic diagrammatic construction (ADC(2)) calculations using the resolution of the identity (RI) method have been performed on poly-(p-phenylenevinylene) (PPV) oligomers with chain lengths up to eight phenyl rings. Vertical excitation energies for the four lowest π–π* excitations and geometry relaxation effects for the lowest excited state (S1) are reported. Extrapolation to infinite chain length shows good agreement with analogous data derived from experiment. Analysis of the bond length alternation (BLA) based on the optimized S1 geometry provides conclusive evidence for the localization of the defect in the center of the oligomer chain. Torsional potentials have been computed for the four excited states investigated and the transition densities divided into fragment contributions have been used to identify excitonic interactions. The present investigation provides benchmark results, which can be used (i) as reference for lower level methods and (ii) give the possibility to parametrize an effective Frenkel exciton Hamiltonian for quantum dynamical simulations of ultrafast exciton transfer dynamics in PPV type systems.
登录
查看更多内容
影响因子：
4.4
作者：
Hättig, C
通讯作者：
Hättig, C
影响因子：
3.3
作者：
Beenken, WJD;Pullerits, T
通讯作者：
Pullerits, T
影响因子：
4.4
作者：
Hättig, C;Weigend, F
通讯作者：
Weigend, F
DOI：
10.1142/s0219633610005645
发表时间：
2010-02-01
影响因子：
2.4
作者：
Lukes, Vladimir;Solc, Roland;Kauffmann, Harald-Friedrich
通讯作者：
Kauffmann, Harald-Friedrich
影响因子：
4.4
作者：
Gierschner, J;Mack, HG;Oelkrug, D
通讯作者：
Oelkrug, D