MPP的线性光谱和非线性光谱的物理机制

doi:10.12422/j.issn.1672-6952.2026.03.006

摘要/Abstract

摘要：

运用量子化学计算和波函数分析方法，从理论上研究了三角形大环金（I）?联苯配合物异构体（MPP）的电子结构和光化学性质，探究了其线性与非线性光谱的物理机制；通过最高已占轨道（HOMO）?最低未占轨道（LUMO）分子轨道分析，以及态密度（DOS）、单光子吸收光谱（OPA）、静态及280 nm的共振拉曼光谱等线性光谱进行表征，揭示了MPP的电子激发特性与分子振动对线性光谱的调控规律；基于电荷差分密度图（CDD）和跃迁密度矩阵（TDM）的可视化方法研究了MPP的电子激发特性，明确了电荷转移和局域激发现象对光学响应的影响；通过计算分子（超）极化率表征MPP的非线性光谱核心物理特征，研究了其非线性光学响应规律。结果表明，MPP 线性光谱在280 nm 处存在强吸收峰，且分子振动模式对拉曼光谱特征具有显著的调控作用；在非线性光学方面则具有显著的非线性各向异性特征，并且（超）极化率随波长的增加而减小。

关键词: 单光子吸收, 拉曼活性, 电荷转移, （超）极化率, 密度泛函理论

Abstract:

This study theoretically investigates the electronic structures and photophysical properties of isomeric triangular macrocyclic gold(I)?biphenylene complex (MPP) using quantum chemical calculations and wavefunction analysis methods，aiming to elucidate the physical mechanisms underlying their linear and nonlinear optical spectra.The molecular orbital characteristics were analyzed via highest occupied molecular orbital (HOMO)?lowest unoccupied molecular orbital (LUMO) analysis，density of states (DOS)，one?photon absorption (OPA) spectrum，as well as static and 280 nm resonance Raman spectra， thereby revealing the regulatory mechanisms of electronic excitation features and molecular vibrations on linear spectral properties. The electron excitation characteristics of MPP were further visualized using charge difference density (CDD) maps and transition density matrix (TDM)，clarifying the influence of charge transfer and localized excitations on optical responses.Additionally，the core physical features of nonlinear optical behaviors were characterized by computing molecular (hyper)polarizability to explore its nonlinear optical response patterns.Results demonstrate that MPP exhibits a strong absorption peak at 280 nm in linear spectra， with molecular vibrational modes significantly modulating Raman spectral features.In nonlinear optical aspects，MPP shows pronounced nonlinear anisotropic characteristics，and the (hyper)polarizability decreases with increasing wavelength.

Key words: One?photon absorption, Raman activity, Charge transfer, (Hyper)Polarizability, Density Functional Theory

中图分类号:

TQ591

周悦, 赵波, 王金刚. MPP的线性光谱和非线性光谱的物理机制[J]. 辽宁石油化工大学学报, 2026, 46(3): 42-50.

Yue ZHOU, Bo ZHAO, Jingang WANG. Physical Mechanisms of Linear and Nonlinear Optical Spectra of MPP[J]. Journal of Liaoning Petrochemical University, 2026, 46(3): 42-50.

图/表 12

图1 MPP结构的三维图

Fig.1 Three?dimensional diagram of MPP structure

图2 MPP的HOMO?LUMO轨道图

Fig.2 HOMO?LUMO orbital diagram of MPP

图3 MPP的TDOS和PDOS曲线

Fig.3 The TDOS and PDOS curves of MPP

图4 MPP的紫外?可见光吸收光谱图

Fig.4 UV?vis absorption spectra of MPP

图5 MPP在S2、S3激发下的TDM图和CDD图注：图中蓝色代表空穴，红色代表电子，下同。

Fig.5 The TDM and CDD graph of MPP under S2, S3 excitation

图6 MPP在S67、S78激发下的TDM图和CDD图

Fig.6 The TDM and CDD graph of MPP under S67, S78 excitation

图7 不同激发态下MPP的Cele?Chole等值面图

Fig.7 The Cele?Chole equivalence surface plots of MPP under different excited states

表1 主要OPA激发态的跃迁指数

Table 1 Transition index of the main OPA excited states

激发态	H指数	D指数/Å	t指数	S_r 指数	激发能/eV	空穴离域指数	电子离域指数
S₀→S₂	6.147	0.603	-3.028	0.695	4.403	4.38	2.33
S₀→S₃	5.973	0.027	-3.911	0.717	4.417	4.07	2.29
S₀→S₆₇	6.141	0.180	-4.432	0.703	5.868	3.88	2.05
S₀→S₇₈	4.668	1.116	-2.186	0.683	6.039	5.72	2.50

图 8 MPP的静态拉曼光谱和共振拉曼光谱（a）静态拉曼光谱（b）共振拉曼光谱

Fig.8 Static Raman and resonance Raman spectra of MPP

图 9 MPP在静态拉曼光谱中的振动模式（a） 1 313.6 cm-1 （b） 3 038.7 cm-1

Fig.9 Vibrational mode of MPP at static Raman spectrum

图 10 MPP在280 nm共振拉曼光谱中的振动模式

Fig.10 Vibrational mode of MPP at inresonance Raman spectrum at 280 nm

图11 MPP在不同波长下的（超）极化率及其单位球面表示

Fig.11 The(hyper)polarizability of MPP at different wavelengths and its unit spherical surface representation

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