Third‐Order Nonlinear Optical Properties of One‐Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups

Kishi, Ryohei; Katsurayama, Tsubasa; Ochi, Shoki; Makino, Akihiro; Matsushita, Naoyuki; Saito, Michika; Nagami, Takanori; Fujiyoshi, Jun Ya; Nakano, Masayoshi

doi:10.1002/open.201700083

Cited by 3 publications

(3 citation statements)

References 63 publications

(92 reference statements)

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“…56 Usually this correlation effect has huge impact, 57 especially on higher order NLOPs. 11,[58][59][60][61][62] The formation of C 6 H 4 diradical from C 6 H 6 decreases the longitudinal CCSD α zz by approximately 5.3 a.u. However, the PNOC analysis reveals that in fact the contribution of the occupied σtype NOs increases by 6.0 a.u., and the lowering of the linear response is observed due to the virtual σ and occupied and virtual π-type orbitals.…”

Section: Orbital Contributions To Nlops In Benzene and Pbenzynementioning

confidence: 99%

Partition of optical properties into orbital contributions

Sitkiewicz

Rodríguez‐Mayorga

Luis

et al. 2019

Phys. Chem. Chem. Phys.

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Nonlinear optical properties (NLOPs) play a major role in photonics, electro-optics and optoelectronics, and other fields of modern optics. The design of new NLO molecules and materials has benefited from the development of computational tools to analyze the relationship between the electronic structure of molecules and its optical response. In this paper, we present a new means to analyze the response property through the partition of NLOPs in terms of orbital contributions (PNOC). This tool can be used to obtain a local representation of the NLOPs, providing a powerful visualization aid to connect the magnitude of the optical property with some parts of the molecule. Unlike other methods to analyze NLOPs, the PNOC decomposes the optical property into orbitals of the unperturbed system, furnishing this method with the ability to assess the performance of single-and multi-determinant electronic structure methods. PNOC can be also used to design small basis sets for an accurate description of large systems, saving a substantial amount of computer time for the calculation of optical properties.

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Section: Orbital Contributions To Nlops In Benzene and Pbenzynementioning

confidence: 99%

Partition of optical properties into orbital contributions

Sitkiewicz

Rodríguez‐Mayorga

Luis

et al. 2019

Phys. Chem. Chem. Phys.

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show abstract

“…For example, Kishi et al reported the linear and thirdorder NLO polarizability of phenoxyl-based derivatives of quinoidal oligothiophenes. 36 Similarly, Vikramaditya et al reviewed the electronic structure−property relationship of αoligothiophenes substituted with electron-donating and electron-withdrawing groups. 37 Dependence of linear and third-order NLO polarizability of oligothiophenes upon the type, number, and position of different substituents was explored by van Keuren et al 38 An in-depth interpretation of NLO properties at both microscopic and macroscopic levels is required for the establishment of efficient materials to be used in NLO devices.…”

Section: Introductionmentioning

confidence: 99%

“…Over the last several decades, many quinoidal oligothiophene derivatives were reported to have NLO response characteristics. For example, Kishi et al reported the linear and third-order NLO polarizability of phenoxyl-based derivatives of quinoidal oligothiophenes . Similarly, Vikramaditya et al reviewed the electronic structure–property relationship of α-oligothiophenes substituted with electron-donating and electron-withdrawing groups .…”

Section: Introductionmentioning

confidence: 99%

Chemically Modified Quinoidal Oligothiophenes for Enhanced Linear and Third-Order Nonlinear Optical Properties

et al. 2021

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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.

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Tunability of Open‐Shell Character, Charge Asymmetry, and Third‐Order Nonlinear Optical Properties of Covalently Linked (Hetero)Phenalenyl Dimers

Minamida

Kishi

Fukuda

et al. 2018

Chemistry A European J

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Tunability of the open-shell character, charge asymmetry, and third-order nonlinear optical (NLO) properties of covalently linked (hetero)phenalenyl dimers are investigated by using the density functional theory method. By changing the molecular species X and substitution position (i, j) for the linker part, a variety of intermonomer distances R and relative alignments between the phenalenyl dimers can be realized from the geometry optimizations, resulting in a wide-range tuning of diradical character y and charge asymmetry. It is found that the static second hyperpolarizabilities along the stacking direction, γ , are one-order enhanced for phenalenyl dimer systems exhibiting intermediate y, a feature that is in good agreement with the "y-γ correlation". By replacing the central carbon atoms of the phenalenyl rings with a boron or a nitrogen, we have also designed covalently linked heterophenalenyl dimers. The introduction of such a charge asymmetry to the open-shell systems, which leads to closed-shell ionic ground states, is found to further enhance the γ values of the systems having longer intermonomer distance R with intermediate ionic character, that is, charge asymmetry. The present results demonstrate a promising potential of covalently linked NLO dimers with intermediate open-shell/ionic characters as a new building block of highly efficient NLO systems.

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Third‐Order Nonlinear Optical Properties of One‐Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups

Cited by 3 publications

References 63 publications

Partition of optical properties into orbital contributions

Partition of optical properties into orbital contributions

Chemically Modified Quinoidal Oligothiophenes for Enhanced Linear and Third-Order Nonlinear Optical Properties

Tunability of Open‐Shell Character, Charge Asymmetry, and Third‐Order Nonlinear Optical Properties of Covalently Linked (Hetero)Phenalenyl Dimers

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