Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π‑Radicals

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-10, Vol.128 (39), p.8473-8482
• Main Authors: Shoda, Jinki, Yokoyama, Masako, Yoshida, Wataru, Matsui, Hiroshi, Sugimori, Ryota, Kishi, Ryohei, Kitagawa, Yasutaka
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c05200

This paper theoretically investigated the correlation between the open-shell electronic structure and third-order nonlinear optical (NLO) properties of one-dimensional (1D) stacked chains of π-radicals. By employing the finite N-mer models consisting of methyl or phenalenyl radicals with different stacking distances, we evaluated the average and standard deviation of diradical characters y i for N-mer models of π-radicals (y av and y SD). Then, we estimated these diradical characters at the limit of N → ∞. These y-based indices were helpful in discussing the correlation between the open-shell electronic structures and the second hyperpolarizability per dimer at the limit N → ∞, γ∞ for the 1D chains with stacking distance alternation (SDA). The calculated γ∞ values and the polymer/dimer ratio γ∞/γ­(N = 2) were enhanced significantly when both the stacking distance and SDA are small. We also found that the spin-unrestricted long-range-corrected (LC−)­UBLYP method with the range-separating parameter μ = 0.47 bohr–1 well reproduced the trend of γ∞ of this type of 1D chain estimated at the spin-unrestricted coupled-cluster levels. The present study is expected to contribute to establishing the design guidelines for future high-performance open-shell molecular NLO materials.