Universal Exciton Size in Organic Polymers is Determined by Nonlocal Orbital Exchange in Time-Dependent Density Functional Theory

被引：55

作者：

Mewes, Stefanie A. ^{[1
]}

Plasser, Felix ^{[2
]}

Dreuw, Andreas ^{[1
]}

机构：

[1] Ruprecht Karls Univ Heidelberg, Interdisciplinary Ctr Sci Comp, Neuenheimer Feld 205A, D-69120 Heidelberg, Germany

[2] Univ Vienna, Fac Chem, Inst Theoret Chem, Wahringerstr 17, A-1090 Vienna, Austria

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2017年 / 8卷 / 06期

关键词：

TAMM-DANCOFF APPROXIMATION; PI-CONJUGATED SYSTEMS; CHARGE-TRANSFER; POLARIZATION PROPAGATOR; ELECTRONIC EXCITATIONS; STATES; THERMOCHEMISTRY; MOLECULES; SCHEME;

D O I：

10.1021/acs.jpclett.7b00157

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The exciton size of the lowest singlet excited state in a diverse set of organic pi-conjugated polymers is studied and found to be a universal, system-independent quantity of approximately 7 A in the single-chain picture. With time-dependent density functional theory (TDDFT), its value as well as the overall description of the exciton is almost exclusively governed by the amount of nonlocal orbital exchange. This is traced back to the lack of the Coulomb attraction between the electron and hole quasiparticles in pure TDDFT, which is reintroduced only with the admixture of nonlocal orbital exchange.

引用

页码：1205 / 1210

页数：6

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