Size dependence of optical nonlinearity for H-capped carbon chains, H-(CC)n-H (n = 3-15): analysis of its nature and prediction for long chains

Zeyu Liu; Jiaojiao Wang; Qing Zhou; Tian Lu; Xia Wang; Xiufen Yan; Mengdi Zhao; Aihua Yuan

doi:10.1039/d3cp04150f

Size dependence of optical nonlinearity for H-capped carbon chains, H-(CC)_n-H (n = 3-15): analysis of its nature and prediction for long chains

Phys Chem Chem Phys. 2023 Nov 1;25(42):29165-29172. doi: 10.1039/d3cp04150f.

Authors

Zeyu Liu¹, Jiaojiao Wang¹, Qing Zhou¹, Tian Lu², Xia Wang¹, Xiufen Yan¹, Mengdi Zhao³, Aihua Yuan¹

Affiliations

¹ School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, People's Republic of China. liuzy@just.edu.cn.
² Beijing Kein Research Center for Natural Sciences, Beijing 100022, People's Republic of China. sobereva@sina.com.
³ Department of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, People's Republic of China.

PMID: 37870160
DOI: 10.1039/d3cp04150f

Abstract

Based on a computational approach that can accurately describe their geometric structures and electronic spectra, we have theoretically studied the nonlinear optical (NLO) properties of H-capped carbon chains, H-(CC)_n-H (n = 3-15), for the first time. Special attention was paid to the size dependence of the molecular (hyper)polarizability of these species through the nonlinear fitting of the data, which formed two power-law formulas of α_iso(∞) = -0.206 + 0.264n^1.498 and γ_‖(∞) = -0.624 + 0.006n^3.368 and was thoroughly discussed at the electronic structure level by in-depth wavefunction analyses. The fundamental gap (ΔE) between vertical ionization energy (VIE) and vertical electron affinity (VEA) is found to be related to the molecular (hyper)polarizability. The calculated (hyper)polarizability of the carbon chains H-(CC)_n-H (n = 3-15) is more sensitive to the density functional theory (DFT) applied than to the basis set selected. The results are expected to provide theoretical guidance for the property prediction of arbitrarily long carbon chains not yet synthesized.