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Singlet-Fission-Induced Enhancement of Third-Order Nonlinear Optical Properties of Pentacene Dimers.

ABSTRACT: Using quantum chemical calculations and exciton dynamics simulations, we investigate the static second hyperpolarizability ? [the third-order nonlinear optical (NLO) property at the molecular scale] of slip-stacked pentacene dimer models in the correlated-triplet-pair [1(TT)] state created from the singlet excited state in the singlet fission (SF) process. It is found that the SF induces significant (?20 times at maximum) enhancement of ?/monomer in the 1(TT) state as compared to that in the singlet ground state. The origin of the remarkable enhancement of ?/monomer is revealed by analyzing the ? density distribution and the intermolecular orbital interaction. Furthermore, we clarify molecular packings suitable for highly efficient SF and largely enhanced ? values of a novel class of SF-induced NLO systems, which have promising potential to surpass the conventional NLO systems.

SUBMITTER: Tonami T

PROVIDER: S-EPMC6777123 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Singlet-Fission-Induced Enhancement of Third-Order Nonlinear Optical Properties of Pentacene Dimers.

Tonami Takayoshi T Nagami Takanori T Okada Kenji K Yoshida Wataru W Nakano Masayoshi M

ACS omega 20190920 14

Using quantum chemical calculations and exciton dynamics simulations, we investigate the static second hyperpolarizability γ [the third-order nonlinear optical (NLO) property at the molecular scale] of slip-stacked pentacene dimer models in the correlated-triplet-pair [<sup>1</sup>(TT)] state created from the singlet excited state in the singlet fission (SF) process. It is found that the SF induces significant (∼20 times at maximum) enhancement of γ/monomer in the <sup>1</sup>(TT) state as compa ...[more]

PMID: 31592485

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Project description:In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (αiso) polarizability value of 603.1 × 10-24 esu is shown by compound 7 which is ∼12, ∼16, ∼9, ∼11, ∼10, and ∼4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability ⟨γ⟩ with an amplitude of 7607 × 10-36 esu at the M06/6-311G** level of theory, which is ∼521, ∼505, ∼38, ∼884, ∼185, and ∼15 times more than that of compounds 1-6, respectively. The extensively larger ⟨γ⟩ amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications.

Project description:The process of singlet fission (SF) produces two triplet excited states (T1 + T1) from one singlet excited exciton (S1) and a molecule in its ground state (S0). It, thus, possesses the potential to boost the solar cell efficiency above the thermodynamic Shockley-Queisser limit of 33%. A key intermediate in the SF mechanism is the singlet correlated triplet pair state 1(T1T1). This state is of great relevance, as its formation is spin-allowed and, therefore, very fast and efficient. Three fundamentally different pathways to formation of 1(T1T1) have been documented so far. The factors that influence which mechanism is associated with which chromophore, however, remain largely unknown. In order to harvest both triplet excitons independently, a decorrelation of the correlated triplet pair state to two individual triplets is required. This second step of the SF process implies a change in the total spin quantum number. In the case of a dimer, this is usually only possible if the coupling between the two pentacenes is sufficiently weak. In this study, we present two platinum-bridged pentacene dimers in which the pentacenes are coupled strongly, so that spin-decorrelation yielding (T1 + T1) was initially expected to be outcompeted by triplet-triplet annihilation (TTA) to the ground state. Both platinum-bridged pentacene dimers undergo quantitative formation of the (T1T1) state on a picosecond timescale that is unaffected by the internal heavy-atom effect of the platinum. Instead of TTA of (T1T1) to the ground state, the internal heavy-atom effect allows for 1(T1T1)-3(T1T1) and 1(T1T1)-5(T1T1) mixing and, thus, triggers subsequent TTA to the (T1S0) state and minor formation of (T1 + T1). A combination of transient absorption and transient IR spectroscopy is applied to investigate the mechanism of the (T1T1) formation in both dimers. Using a combination of experiment and quantum chemical calculations, we are able to observe a transition from the CT-mediated to the direct SF mechanism and identify relevant factors that influence the mechanism that dominates SF in pentacene. Moreover, a combination of time-resolved optical and electron paramagnetic resonance spectroscopic data allows us to develop a kinetic model that describes the effect of enhanced spin-orbit couplings on the correlated triplet pair state.

Dataset Information

Singlet-Fission-Induced Enhancement of Third-Order Nonlinear Optical Properties of Pentacene Dimers.

Publications

Singlet-Fission-Induced Enhancement of Third-Order Nonlinear Optical Properties of Pentacene Dimers.

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