Makkonen Esko, Rossi Tuomas P, Larsen Ask Hjorth, Lopez-Acevedo Olga, Rinke Patrick, Kuisma Mikael, Chen Xi
Department of Applied Physics, Aalto University, Espoo, Finland.
Simune Atomistics S.L., Donostia-San Sebastián, Spain.
J Chem Phys. 2021 Mar 21;154(11):114102. doi: 10.1063/5.0038904.
Electronic circular dichroism (ECD) is a powerful spectroscopy method for investigating chiral properties at the molecular level. ECD calculations with the commonly used linear-response time-dependent density functional theory (LR-TDDFT) framework can be prohibitively costly for large systems. To alleviate this problem, we present here an ECD implementation within the projector augmented-wave method in a real-time-propagation TDDFT framework in the open-source GPAW code. Our implementation supports both local atomic basis sets and real-space finite-difference representations of wave functions. We benchmark our implementation against an existing LR-TDDFT implementation in GPAW for small chiral molecules. We then demonstrate the efficiency of our local atomic basis set implementation for a large hybrid nanocluster and discuss the chiroptical properties of the cluster.
电子圆二色光谱（ECD）是一种在分子水平上研究手性性质的强大光谱方法。对于大型系统，使用常用的线性响应含时密度泛函理论（LR-TDDFT）框架进行ECD计算成本过高。为缓解这一问题，我们在此展示了一种在开源GPAW代码的实时传播TDDFT框架下，基于投影增强波方法的ECD实现。我们的实现支持局部原子基组和波函数的实空间有限差分表示。我们针对GPAW中现有的LR-TDDFT实现，对小型手性分子的ECD实现进行了基准测试。然后，我们展示了局部原子基组实现在大型混合纳米团簇上的效率，并讨论了该团簇的圆二色性质。
