The low-lying excited states of neutral polyacenes and their radical cations: a quantum chemical study employing the algebraic diagrammatic construction scheme of second order

Knippenberg, Stefan; Starcke, Jan Hendrik; Wormit, Michael; Dreuw, Andreas

doi:10.1080/00268976.2010.526643

Cited by 50 publications

(59 citation statements)

References 85 publications

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“…This has been observed, for example, in linearly fused polyacenes where, with increasing molecular size, states with a dominant double excitation character fall into the low-energy region of the excitation spectrum [58,68,69]. They then become relevant for a comprehensive description of the photochemistry of the molecules.…”

Section: Excited Electronic States With Large Double Excitation Charamentioning

confidence: 97%

The Art of Choosing the Right Quantum Chemical Excited‐State Method for Large Molecular Systems

Harbach¹,

Dreuw²

2011

Modeling of Molecular Properties

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Section: Excited Electronic States With Large Double Excitation Charamentioning

confidence: 97%

The Art of Choosing the Right Quantum Chemical Excited‐State Method for Large Molecular Systems

Harbach¹,

Dreuw²

2011

Modeling of Molecular Properties

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“…The ground state is already difficult to describe, let alone the more challenging excited states (58)(59)(60)(61)(62)(63). As a result of a "charge separation in disguise" (61,64), time-dependent density functional theory (TDDFT) is known to greatly underestimate the 1 B 2u excitation (65,66), which is the lowest bright excitation for acenes longer than 2, and is characterized by one electron promoted from the highest occupied molecular orbital to the lowest unoccupied molecular orbital (HOMO→LUMO).…”

Section: Significancementioning

confidence: 99%

Nature of ground and electronic excited states of higher acenes

Yang

Davidson

Yang

2016

Proc. Natl. Acad. Sci. U.S.A.

174

208

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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 particleparticle 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 3 B 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 1 B 2u is a zwitterionic state to the short axis. The excited 1 A g state gradually switches from a doubleexcitation state to another zwitterionic state to the short axis, but always keeps its covalent nature to the long axis. An energy crossing between the 1 B 2u and excited 1 A g 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.higher acenes | diradical | double excitation | particle-particle random-phase approximation | charge-transfer excitation

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“…7 Low-lying excited states in polyenes with significant double-excitation character are notable examples in which the single excitation picture fails qualitatively to describe the system. [45][46][47][48][49][50][51][52] Strong double-excitation features in XANES spectroscopy have been reported for ferrocene and ferrocenium compounds, 53 and it has been shown that double or higher-order excited configurations are necessary to construct the spin-symmetry-adapted wavefunctions of molecules with open-shell ground states. [54][55][56][57] Formally any state with energy close to the sum of two single excitation energies can be considered a double excitation.…”

Section: Electronic Structure Simulations Of Double Excitationsmentioning

confidence: 99%

“…59 These include complete active space self-consistent field (CASSCF), complete active space perturbation theory of second order (CASPT2), 51 coupled cluster (CC), 60 multireference configuration interaction (MRCI), 52,61 symmetry-adapted cluster configuration interaction (SAC-CI), 62 algebraic diagrammatic construction (ADC), [48][49][50] and multireference Møller-Plesset perturbation theory (MRMP). 46,58 These accurate techniques are computationally expensive and limited to small molecular systems such as polyenes with several carbon atoms.…”

Section: Electronic Structure Simulations Of Double Excitationsmentioning

confidence: 99%

Double-core excitations in formamide can be probed by X-ray double-quantum-coherence spectroscopy

Zhang

Healion

Biggs

et al. 2013

The Journal of Chemical Physics

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The attosecond, time-resolved X-ray double-quantum-coherence four-wave mixing signals of formamide at the nitrogen and oxygen K-edges are simulated using restricted excitation window time-dependent density functional theory and the excited core hole approximation. These signals, induced by core exciton coupling, are particularly sensitive to the level of treatment of electron correlation, thus providing direct experimental signatures of electron and core-hole manybody effects and a test of electronic structure theories.

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The low-lying excited states of neutral polyacenes and their radical cations: a quantum chemical study employing the algebraic diagrammatic construction scheme of second order

Cited by 50 publications

References 85 publications

The Art of Choosing the Right Quantum Chemical Excited‐State Method for Large Molecular Systems

The Art of Choosing the Right Quantum Chemical Excited‐State Method for Large Molecular Systems

Nature of ground and electronic excited states of higher acenes

Double-core excitations in formamide can be probed by X-ray double-quantum-coherence spectroscopy

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