MOE Key Laboratory of Organic OptoElectronics and Molecular Engineering, Department of Chemistry , Tsinghua University , Beijing 100084 , People's Republic of China.
Division of Chemistry and Chemical Engineering , California Institute of Technology , Pasadena , California 91125 , United States.
J Chem Theory Comput. 2018 Oct 9;14(10):5027-5039. doi: 10.1021/acs.jctc.8b00628. Epub 2018 Sep 6.
We implement and apply time-dependent density matrix renormalization group (TD-DMRG) algorithms at zero and finite temperature to compute the linear absorption and fluorescence spectra of molecular aggregates. Our implementation is within a matrix product state/operator framework with an explicit treatment of the excitonic and vibrational degrees of freedom, and it uses the locality of the Hamiltonian in the zero-exciton space to improve the efficiency and accuracy of the calculations. We demonstrate the power of the method by calculations on several molecular aggregate models, comparing our results against those from multilayer multiconfiguration time-dependent Hartree and n-particle approximations. We find that TD-DMRG provides an accurate and efficient route to calculate the spectrum of molecular aggregates.
我们在零温及有限温条件下实现并应用含时密度矩阵重整化群（TD-DMRG）算法来计算分子聚集体的线性吸收和荧光光谱。我们的实现是基于矩阵乘积态/算符框架，并对激子和振动自由度进行显式处理，同时利用哈密顿量在零激子空间的局域性来提高计算的效率和准确性。我们通过对几个分子聚集体模型的计算展示了该方法的强大功能，并将我们的结果与多层多组态含时哈特ree 方法和 n-粒子近似方法的结果进行了比较。我们发现 TD-DMRG 为计算分子聚集体的光谱提供了一种准确而高效的途径。
