Three-dimensional representation of the pure electric-dipole and the mixed first hyperpolarizabilities: The modified unit sphere representation

IF 3.4 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Andrea Bonvicini, Benoît Champagne
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引用次数: 0

Abstract

In this work, the theory of the modified unit sphere representation (mUSR) has been proposed as a computational tool suitable for the three-dimensional representation of the pure electric-dipole [ β λ μ ν ( 2 ω ; ω , ω ) ] as well as of the mixed electric-dipole/magnetic-dipole [ α J λ μ ν ( 2 ω ; ω , ω ) and β J λ μ ν ( 2 ω ; ω , ω ) ] or electric-dipole/electric-quadrupole [ α K λ μ ν o ( 2 ω ; ω , ω ) and β K λ μ ν o ( 2 ω ; ω , ω ) ] first hyperpolarizabilities. These five quantities are Cartesian tensors and they are responsible for the chiral signal in the chiroptical version of the hyper-Rayleigh scattering (HRS) spectroscopy, namely the HRS optical activity (HRS-OA) spectroscopy. For the first time, for each hyperpolarizability, alongside with the three-dimensional representation of the whole (i.e., reducible) Cartesian tensors, the mUSRs are developed for each of the irreducible Cartesian tensors (ICTs) that constitute them. This scheme has been applied to a series of three (chiral) hexahelicene molecules containing different degrees of electron-withdrawing (quinone) groups and characterized by the same (positive) handedness. For these molecules, the mUSR shows that, upon substitution, the most remarkable qualitative and semi-quantitative (enhancement of the molecular responses) effects are obtained for the pure electric-dipole and for the mixed electric-dipole/magnetic-dipole hyperpolarizabilities.

纯电偶极子和混合第一超极化率的三维表示法:修正的单位球表示法
在这项工作中,提出了修正单位球表示(mUSR)理论,作为适合纯电偶极子 [ β λ μ ν ( - 2 ω ;ω , ω ) $$ {\beta}_{\lambda \mu \nu}\left(-2\omega; \omega, \omega \right) $$ ]以及混合电偶极子/磁偶极子 [ α J λ μ ν ( - 2 ω ; ω , ω ) $$ {}^{\alpha }{J}_{\lambda \mu \nu}\left(-2\omega, \omega, \omega \right) $$ ];\omega, \omega \right) $$ 和 β J λ μ ν ( - 2 ω ; ω , ω ) $$ {}^{\beta }{J}_{lambda \mu \nu}\left(-2\omega; \omega, \omega \right) $$ ] 或电偶极子/电四极子 [ α K λ μ ν o ( - 2 ω ;ω , ω ) $$ {}^{α }{K}_{\lambda \mu \nu o}\left(-2\omega; \omega, \omega \right) $$ 和 β K λ μ ν o ( - 2 ω ;ω , ω ) $$ {}^{\beta }{K}_{\lambda \mu \nu o}\left(-2\omega; \omega, \omega \right) $$ ] 第一超极化率。这五个量是笛卡尔张量,它们在超瑞利散射(HRS)光谱的气韵学版本,即 HRS 光学活动(HRS-OA)光谱中负责手性信号。除了整个(即可还原的)笛卡尔张量的三维表示之外,还首次针对每个超极化率,为构成它们的每个不可还原笛卡尔张量(ICTs)开发了 mUSRs。这一方案已被应用于一系列含有不同程度的抽电子(醌)基团并具有相同(正)手性特征的三种(手性)六烯分子。对于这些分子,mUSR 显示,在发生置换时,纯电偶极性和电偶极性/磁偶极性混合超极化率会产生最显著的定性和半定量(分子反应增强)效应。
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来源期刊
CiteScore
6.60
自引率
3.30%
发文量
247
审稿时长
1.7 months
期刊介绍: This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.
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