外电场下 5-溴-2-氟硝基苯分子的解离及激发特性

doi:10.3969/j.issn.1007-5461.2025.03.002

摘要/Abstract

摘要： 本文采用密度泛函理论 (DFT) 中的B3LYP/6-311+G(d,p)方法, 探究了强度范围为0~0.040 arb. units的外加电场对5-溴-2-氟硝基苯 (5Br2FNB) 分子的结构参数、自然键轨道电荷布局、电偶极矩、能隙及势能曲线等的影响。还利用含时密度泛函理论 (TD-DFT) 中的B3LYP/6-311+G(d,p)方法, 对该分子在不同外电场下的激发能和空穴-电子进行了分析。研究结果表明, 随着外电场强度的增加, 5Br2FNB分子中的C(5)-Br(10)键增长, Br(10)原子电负性增强, 最高占据分子轨道 (HOMO) 的能量和最低未占据分子轨道 (LUMO) 的能量、能隙、激发能和势垒均呈现整体下降趋势, 表明分子稳定性在逐渐减弱。并且当外电场强度超过0.030 arb. units时, 各项分析均显示C(5)-Br(10)键已经发生解离。通过对5Br2FNB分子空穴-电子分析可知, 当外电场强度范围为0~0.010 arb. units时, 分子的S0→S1为局域激发; 当外电场强度范围为0.020~0.030 arb. units时, S0→S1为电荷转移激发; 当外电场强度为0.040 arb. units时, S0→S1 又重新转变成局域激发, 这意味着C(5)-Br(10)键断裂后分子的电荷开始重新分配, 进一步证实了外电场强度达到 0.030 arb. units时C(5)-Br(10)键已经开始解离。本研究对于深入了解5Br2FNB分子在外电场作用下的解离机理具有重要参考价值。

关键词: 光谱学, 5-溴-2-氟硝基苯, 密度泛函理论, 外电场, 解离, 空穴-电子分析

Abstract: The effects of external electric field (0-0.040 arb. units) on the structure parameter, natural bond orbital charge distribution, electric dipole moment, energy gap and potential energy curve of 5- bromo-2-fluoronitrobenzene (5Br2FNB) molecule were investigated by using DFT/B3LYP/6-311+G(d,p) method in this work. The excitation energy and hole-electron of the molecule under different external electric fields were also studied by TD-DFT/B3LYP/6-311+G(d,p) method. The results show that, with the increase of external electric field intensity, the bond length of C(5)-Br(10) and the electronegativity of Br(10) atom increases, and the HOMO and LUMO energy, energy gap, excitation energy and potential barrier all show an overall decreasing trend, indicating that the stability of the molecule decreases gradually. All the analyses indicate that C(5)-Br(10) bond dissociation has occurred when the external electric field intensity exceeds 0.030 arb. units. According to the hole-electron analysis, it is shown that when the external electric field intensity range is 0-0.010 arb. units, the S0→S1 excitation of the molecule is local excitation, and when the external electric field intensity range is 0.020-0.030 arb. units, S0→S1 is charge transfer excitation. However, when the external electric field is 0.040 arb. units, S0→S1 transforms again into local excitation, which means that the charges of molecule begin to redistribute after the C(5)- Br(10) bond breakage, further confirming that the C(5) -Br(10) bond begins to dissociate when the external electric field intensity reaches 0.030 arb. units. This study has important reference value for deeper understanding of the dissociation mechanism of 5Br2FNB molecule under external electric fields.

Key words: spectroscopy, 5-bromo-2-fluoronitrobenzene, density functional theory, external electric field, dissociation, hole-electron analysis

中图分类号:

O561.3

张敏, 秦晨 . 外电场下 5-溴-2-氟硝基苯分子的解离及激发特性[J]. 量子电子学报, 2025, 42(3): 304-312.

ZHANG Min, QIN Chen . Dissociation and excitation properties of 5-bromo-2- fluoronitrobenzene molecule under external electric field[J]. Chinese Journal of Quantum Electronics, 2025, 42(3): 304-312.

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