Hu Weifeng, Chan Garnet Kin-Lic
Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
J Chem Theory Comput. 2015 Jul 14;11(7):3000-9. doi: 10.1021/acs.jctc.5b00174. Epub 2015 Jun 2.
We describe and extend the formalism of state-specific analytic density matrix renormalization group (DMRG) energy gradients, first used by Liu et al. [J. Chem. Theor. Comput. 2013, 9, 4462]. We introduce a DMRG wave function maximum overlap following technique to facilitate state-specific DMRG excited-state optimization. Using DMRG configuration interaction (DMRG-CI) gradients, we relax the low-lying singlet states of a series of trans-polyenes up to C20H22. Using the relaxed excited-state geometries, as well as correlation functions, we elucidate the exciton, soliton, and bimagnon ("single-fission") character of the excited states, and find evidence for a planar conical intersection.
我们描述并扩展了态特异性解析密度矩阵重整化群（DMRG）能量梯度的形式体系，该形式体系最早由Liu等人[《化学理论与计算杂志》2013年，9卷，4462页]使用。我们引入了一种DMRG波函数最大重叠跟踪技术，以促进态特异性DMRG激发态优化。利用DMRG组态相互作用（DMRG-CI）梯度，我们对一系列直至C20H22的反式多烯的低激发单重态进行了弛豫。利用弛豫后的激发态几何结构以及相关函数，我们阐明了激发态的激子、孤子和双磁振子（“单分子裂变”）特性，并找到了平面锥形交叉的证据。
