Excited State Studies of Polyacenes Using the All-Order Constricted Variational Density Functional Theory with Orbital Relaxation

详细信息    查看全文

• 作者：Florian Senn ; Mykhaylo Krykunov
• 刊名：Journal of Physical Chemistry A
• 出版年：2015
• 出版时间：October 22, 2015
• 年：2015
• 卷：119
• 期：42
• 页码：10575-10581
• 全文大小：322K
• ISSN：1520-5215

文摘

For the polyacenes series from naphthalene to hexacene, we present the vertical singlet excitation energies 1 ¹L_a and 1 ¹L_b, as well as the first triplet excitation energies obtained by the all-order constricted variational density functional theory with orbital relaxation (R-CV(鈭?-DFT). R-CV(鈭?-DFT is a further development of variational density functional theory (CV(鈭?-DFT), which has already been successfully applied for the calculation of the vertical singlet excitation energies ¹L_a and ¹L_b for polyacenes,15 and we show that one obtains consistent excitation energies using the local density approximation as a functional for singlet as well as for triplet excitations when going beyond the linear response theory. Furthermore, we apply self-consistent field density functional theory (螖SCF-DFT) and compare the obtained excitation energies for the first triplet excitations T₁, where, due to the character of the transition, 螖SCF-DFT and R-CV(鈭?-DFT become numerically equivalent, and for the singlet excitations 1 ¹L_a and 1 ¹L_b, where the two methods differ.