Describing Excited State Relaxation and Localization in TiO2 Nanoparticles Using TD-DFT.
Describing Excited State Relaxation and Localization in TiO2 Nanoparticles Using TD-DFT.
复制标题
使用 TD-DFT 描述 TiO2 纳米颗粒中的激发态弛豫和局域化。
DOI：
10.1021/ct500787x
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发表时间：
2014
影响因子：
5.5
通讯作者：
Berardo E
中科院分区：
文献类型：
--
作者：
Berardo E
采用含时密度泛函理论（TD-DFT）方法，采用B3 LYP、CAM-B3 LYP和BHLYP三种常用的杂化交换相关（XC）势，研究了裸态和水合态TiO 2纳米粒子的激发态弛豫过程.使用TD-CAM-B3 LYP和TD-BHLYP产生定性相似的结果，所有的结构，这也是符合耦合团簇理论的预测小颗粒。相比之下，TD-B3 LYP被发现做出了相当不同的预测;包括用TD-CAM-B3 LYP和TD-BHLYP都没有观察到的某些粒子的明显圆锥形交叉。与我们之前对垂直激发的观察一致，TD-B3 LYP的问题似乎是TD-B3 LYP和其他没有或低比例的Hartree-Fock交换的XC势的固有趋势，以虚假地稳定电荷转移（CT）状态的能量。即使在水合粒子的情况下，其中垂直激发通常用所有XC势很好地描述，TD-B3 LYP的使用似乎导致某些粒子的激发态弛豫期间的CT问题。我们假设TD-B3 LYP对CT态的虚假稳定化甚至可以驱动激发态优化到与TD-CAM-B3 LYP或TD-BHLYP获得的激发态几何不同的激发态几何。最后，结合TD-CAM-B3 LYP和TD-BHLYP的结果，预测了小的裸露的和水合的TiO 2纳米粒子的激发态弛豫与大的Stokes位移有关.
We have investigated the description of excited state relaxation in naked and hydrated TiO2nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials: B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled-cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree–Fock like exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT problems during excited state relaxation for certain particles. We hypothesize that the spurious stabilization of CT states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries from those obtained using TD-CAM-B3LYP or TD-BHLYP. Finally, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in small naked and hydrated TiO2nanoparticles is predicted to be associated with a large Stokes’ shift.
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影响因子：
9.5
作者：
F. Nunzi;L. Storchi;M. Manca;R. Giannuzzi;G. Gigli;F. De Angelis
通讯作者：
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DOI：
--
发表时间：
2004
期刊：
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通讯作者：
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DOI：
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发表时间：
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期刊：
The Journal of chemical physics
影响因子：
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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影响因子：
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作者：
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