Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 113, Issue 35, Pages E5098-E5107Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1606021113
Keywords
higher acenes; diradical; double excitation; particle-particle random-phase approximation; charge-transfer excitation
Categories
Funding
- Center for the Computational Design of Functional Layered Materials, an Energy Frontier Research Center - US Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012575]
- National Science Foundation [CHE-1362927]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1362927] Funding Source: National Science Foundation
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Higher acenes have drawn much attention as promising organic semiconductors with versatile electronic properties. However, the nature of their ground state and electronic excited states is still not fully clear. Their unusual chemical reactivity and instability are the main obstacles for experimental studies, and the potentially prominent diradical character, which might require a multireference description in such large systems, hinders theoretical investigations. Here, we provide a detailed answer with the particle-particle random-phase approximation calculation. The (1)A(g) ground states of acenes up to decacene are on the closed-shell side of the diradical continuum, whereas the ground state of undecacene and dodecacene tilts more to the open-shell side with a growing polyradical character. The ground state of all acenes has covalent nature with respect to both short and long axes. The lowest triplet state B-3(2u) is always above the singlet ground state even though the energy gap could be vanishingly small in the polyacene limit. The bright singlet excited state B-1(2u) is a zwitterionic state to the short axis. The excited (1)A(g) state gradually switches from a double-excitation state to another zwitterionic state to the short axis, but always keeps its covalent nature to the long axis. An energy crossing between the B-1(2u) and excited (1)A(g)D states happens between hexacene and heptacene. Further energetic consideration suggests that higher acenes are likely to undergo singlet fission with a low photovoltaic efficiency; however, the efficiency might be improved if a singlet fission into multiple triplets could be achieved.
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