丙烯醛在外电场中的解离性质

doi:10.19596/j.cnki.1001-246x.8331

摘要/Abstract

摘要：

利用密度泛函理论（DFT）计算方法，在6-31G+（d，p）基组上，讨论C₃H₄O气体分子在受到外加电场（-10.28 V·nm^-1~10.28 V·nm^-1）作用时的结构特征和解离特性。计算发现，沿分子共轭单键的方向电场增强时，总能量增大，碳碳双键和碳碳单键的键长减小，碳氧双键键长增大，偶极矩减小；能隙E_G增加，红外吸收峰在不同的频率分别发生红移和蓝移，同时IR强度发生变化。分子解离性能表现为：势能壁垒随着外电场增大而降低，达到25.71 V·nm^-1时势能壁垒几乎消失，解离能随着电场增加而逐渐降低，说明在电场作用下解离难度逐渐减小。研究结果为C₃H₄O气体分子或含有该成分的混合物在外电场下的解离特性研究提供参考。

关键词: 丙烯醛, 外电场, 红外光谱, 解离势能面, 降解

Abstract:

Based on HF(Hartree-Fock) calculation method with 3-21G basis set, we discussed structural and dissociation characteristics of C₃H₄O gas molecules under different external fields (from -10.28 V·nm^-1 to 10.28 V·nm^-1). It is found that as the electric field increases along the direction of molecular conjugated single bond the total energy increases. The bond length of C-C double bond and C-C single bond decreases. The bond length of C-O double bond increases. The dipole moment decreases. Energy gap E_G increases. The infrared absorption peak has both red shift and blue shift at different frequencies and the intensity of IR also changes. The molecular dissociation performance is as follows: The potential energy barrier decreases with the increase of the external electric field. As the electric field reaches 25.71 V·nm^-1, the potential energy barrier almost disappears and the dissociation energy decreases gradually with the increase of the electric field, which indicating that the dissociation difficulty of C₃H₄O gas molecules under electric field decreases gradually. It provides reference for the study of dissociation characteristics of C₃H₄O gas molecules or mixtures containing C₃H₄O in external electric field.

Key words: acrolein, external electric field, infrared spectrum, potential energy surface, degradation

中图分类号:

O561
O433

周卓彦, 刘玉柱, 陈宇, 张昕阳, 孙卓怡. 丙烯醛在外电场中的解离性质[J]. 计算物理, 2021, 38(6): 722-728.

Zhuoyan ZHOU, Yuzhu LIU, Yu CHEN, Xinyang ZHANG, Zhuoyi SUN. Dissociation Properties of Acrolein in External Electric Field[J]. Chinese Journal of Computational Physics, 2021, 38(6): 722-728.

图/表 8

图1 无外电场作用下的丙烯醛分子基态结构以及外加电场方向

Fig.1 Ground-state structure of acrolein molecule without external electric field and direction of applied electric field

表1 不同基组和方法优化的C3H4O分子的基态结构

Table 1 Ground state structure of C3H4O molecule optimized with different basis sets and methods

Method	R_{1, 3}/nm	R_{1, 4}/nm	R_{4, 6}/nm	E/Hartree	R²
DFT B3LYP 6-31G+(d, p)	0.121 83	0.147 44	0.134 04	-191.929 92	0.999 978 69
DFT B3LYP 3-21G	0.123 34	0.147 58	0.133 53	-190.850 47	0.999 977 70
DFT B3LYP 6-31G	0.124 14	0.146 78	0.134 29	-191.857 25	0.999 974 866
DFT B3LYP 6-31G+(2d, 2p)	0.121 88	0.147 45	0.134 47	-191.875 48	0.999 976 659
DFT B3LYP 6-31G+(3d, 3p)	0.121 69	0.146 66	0.134 32	-191.748 63	0.999 974 659
Experimental^[18]	0.121 00	0.147 40	0.131 70	-189.699 80

图2 不同外加场下分子能量和偶极矩的变化

Fig.2 Molecular energy and dipole moment as functions of applied field (1 Debye=3.335 64×10-30 C·m)

图3 不同外加场下醛基碳氧双键，碳碳单键和碳碳双键的键长

Fig.3 Bond length of aldehyde CO double bond, CC single bond and CC double bond in external fields

图4 不同外加场下最低空轨道能量EL，最高占据轨道能量EH和能隙EG

Fig.4 Minimum vacant orbital energy EL, maximum occupied orbital energy EH and energy gap EG in external fields

图5 C3H4O在外场下的红外吸收光谱

Fig.5 Infrared absorption spectra of C3H4O in external fields

图6 C3H4O分子共轭碳碳单键在不同电场下的单点扫描势能

Fig.6 Single point scanning potential energy of conjugated CC single bond of C3H4O molecule under different electric fields

图7 以共轭单键与碳氧双键键长为基底不同外场下的分子势能面

Fig.7 Molecular potential energy surfaces with conjugated single bond and CO double bond lengths as bases under different external fields

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