ETH Zürich, Laboratorium für Physikalische Chemie, Vladimir-Prelog-Weg 2, Zürich 8093, Switzerland.
J Chem Theory Comput. 2021 Jun 8;17(6):3320-3334. doi: 10.1021/acs.jctc.0c01048. Epub 2021 May 27.
In this work, we simulate the electron dynamics in molecular systems with the time-dependent density matrix renormalization group (TD-DMRG) algorithm. We leverage the generality of the so-called tangent-space TD-DMRG formulation and design a computational framework in which the dynamics is driven by the exact nonrelativistic electronic Hamiltonian. We show that by parametrizing the wave function as a matrix product state, we can accurately simulate the dynamics of systems including up to 20 electrons and 32 orbitals. We apply the TD-DMRG algorithm to three problems that are hardly targeted by time-independent methods: the calculation of molecular (hyper)polarizabilities, the simulation of electronic absorption spectra, and the study of ultrafast ionization dynamics.
在这项工作中，我们使用含时密度矩阵重整化群（TD-DMRG）算法来模拟分子体系中的电子动力学。我们利用所谓切空间 TD-DMRG 公式的通用性，设计了一个计算框架，其中动力学由精确的非相对论电子哈密顿量驱动。我们表明，通过将波函数参数化为矩阵乘积态，我们可以准确地模拟包括多达 20 个电子和 32 个轨道的系统的动力学。我们将 TD-DMRG 算法应用于三个几乎无法通过时间独立方法来研究的问题：分子（超）极化率的计算、电子吸收光谱的模拟和超快电离动力学的研究。
