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Theoretical Study on Third-Order Nonlinear Optical Properties for One-Hole-Doped Diradicaloids.

ABSTRACT: We investigate the relationships between open-shell character and longitudinal static second hyperpolarizabilities ? for one-hole-doped diradicaloids using the strong-correlated ab initio molecular orbital methods and simple one-dimensional (1D) three-site two-electron (3s-2e) models. As examples of one-hole-doped diradicaloids, we examine H₃ ⁺, methyl radical trimer cation ((CH₃)₃ ⁺), silyl radical trimer cation ((SiH₃)₃ ⁺), and 1,2,3,5-dithiadizolyl trimer cation (DTDA₃ ⁺). For H₃ ⁺, the static ? exhibits negative values and shows a monotonic increase in amplitude with an increase in the open-shell character defined by a neighbor-site interaction (y _S). On the other hand, it is found for (CH₃)₃ ⁺, (SiH₃)₃ ⁺, and DTDA₃ ⁺ that the static ? value exhibits similar behavior to that for H₃ ⁺ up to an intermediate y _S value, while it takes the negative maximum at a large y _S value, followed by a decrease in ? amplitude, and subsequently, ? changes to positive values with a drastic increase for larger y _S values. For example, in DTDA₃ ⁺, the negative/positive ? values, -69 × 10⁵/700 × 10⁵ au at y _S = 0.75/0.87, exhibit significant enhancements in amplitude, 2.4/24 times as large as that (-29 × 10⁵ au) at intermediate y _S = 0.59 as is often the case in DTDA₂. Using the 1D 3s-2e valence-bond configuration interaction model, these sign inversions and drastic increase in the amplitude of ? are found to originate in the differences in Coulomb interactions between valence electrons, between valence and core electrons, and between valence electrons and nuclei. These results contribute to pave the way for the construction of novel control guidelines for the amplitude and sign of ? for one-hole-doped diradicaloids.

SUBMITTER: Yoshida W

PROVIDER: S-EPMC7860065 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Theoretical Study on Third-Order Nonlinear Optical Properties for One-Hole-Doped Diradicaloids.

Yoshida Wataru W Matsui Hiroshi H Miyamoto Hajime H Tonami Takayoshi T Sugimori Ryota R Yoneda Kyohei K Kishi Ryohei R Nakano Masayoshi M

ACS omega 20210108 4

We investigate the relationships between open-shell character and longitudinal static second hyperpolarizabilities γ for one-hole-doped diradicaloids using the strong-correlated ab initio molecular orbital methods and simple one-dimensional (1D) three-site two-electron (3s-2e) models. As examples of one-hole-doped diradicaloids, we examine H3 +, methyl radical trimer cation ((CH3)3 +), silyl radical trimer cation ((SiH3)3</su ...[more]

PMID: 33553922

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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.

Dataset Information

Theoretical Study on Third-Order Nonlinear Optical Properties for One-Hole-Doped Diradicaloids.

Publications

Theoretical Study on Third-Order Nonlinear Optical Properties for One-Hole-Doped Diradicaloids.

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