外电场对CO分子及离子性质的调制和降解

doi:10.19596/j.cnki.1001-246x.8404

摘要/Abstract

摘要：

基于密度泛函理论(DFT)的B3LYP方法，在6-311G++基组水平上，计算研究外加电场下CO分子及离子物理性质，包括总能量、键长、电荷分布、能级分布和红外光谱，并根据势能曲线研究CO外加电场下的降解。随着外电场逐渐增大(- 0.015 a. u.~0.015 a. u.)，CO的性质发生明显的变化, 电场增大到一定程度时可实现CO分子降解。同样，CO⁺离子的总能量随电场的增大逐渐减小，键长变长，偶极矩逐渐变大，分子能隙在Alpha轨道中逐渐减小，在Beta轨道中逐渐增大，红外光谱的强度相应逐渐增大。电场从0.0 a. u增大到0.150 a. u.时，势能曲线的变化同样表明CO⁺离子离解能减小。电场增大到一定程度时可实现CO⁺离子降解。

关键词: 一氧化碳, 密度泛函理论, 降解, 外电场

Abstract:

Based on density functional theory (DFT), a B3LYP method at a level of 6-311G++ was used to study physical properties of CO molecules and ions under applied electric field. Total energy, bond length, charge distribution, energy level distribution and infrared spectrum are studied. Degradation of CO under applied electric field was studied according to its potential energy curve. With gradual increase of external electric field (- 0.015 a.u.~0.015 a.u.), the properties of CO change obviously. As the electric field increases from -0.015 a.u. to 0.145 a.u., the potential energy curve shows that the dissociation energy of CO molecules decreases. CO molecular degradation can be achieved as the electric field increases to a certain extent. Similarly, with the increase of external electric field, total energy of CO ions decreases gradually with the increase of electric field. The bond length becomes longer, the dipole moment becomes greater, and the molecular energy gap decreases gradually in the alpha track and increases in the beta track. The intensity of infrared spectrum increases accordingly. When the electric field increases from 0.0 to 0.150 a. u., the potential energy curve indicates that the dissociation energy of CO ions decreases. CO ion degradation can be achieved as the electric field increases to a certain extent.

Key words: carbon monoxide, density functional theory, degradation, external electric field

吉航, 孙仲谋, 周卓彦, 刘玉柱. 外电场对CO分子及离子性质的调制和降解[J]. 计算物理, 2022, 39(3): 327-334.

Hang JI, Zhongmou SUN, Zhuoyan ZHOU, Yuzhu LIU. Modulation and Degradation of CO Molecular and Ionic Properties with External Electric Field[J]. Chinese Journal of Computational Physics, 2022, 39(3): 327-334.

图/表 17

表1 不同方法优化CO分子基态的结构

Table 1 Structure of CO molecular ground state optimized with different methods

Method	R_e/Å	E/Hartree
B3LYP/6-311G++	1.146 92	-113.300 013
B3LYP/6-311	1.147 32	-113.296 813
BVP86/6-311G++	1.159 46	-113.308 410
BVP86/6-311	1.160 21	-113.305 365
Experimental^[10]	1.128 20

图1 基态CO分子的几何构型(箭头所示为外加电场方向。)

Fig.1 Geometric configuration of CO molecule at ground state (The direction of arrow represents external electric field.)

表2 不同外电场下CO分子的键长和能量及偶极矩

Table 2 Bond lengths, energy and dipole moments of CO molecules under different external electric fields

F/a.u.	E/Hartree	R_e/Å	μ/Debye
-0.015	-113.301 152 69	1.142 07	0.513 9
-0.010	-113.300 353 82	1.143 49	0.299 4
-0.005	-113.299 974 98	1.145 04	0.086 8
0.0	-113.300 013 34	1.146 74	0.124 8
0.005	-113.300 467 33	1.148 59	0.335 9
0.010	-113.301 336 68	1.150 60	0.547 1
0.015	-113.302 622 38	1.152 77	0.759 2

图2 CO分子键长、总能量、偶极矩随外加电场的变化

Fig.2 Variation of CO molecular bond length, total energy and dipole moment with applied electric field

表3 不同外电场下CO+离子的键长和能量及偶极矩

Table 3 Bond lengths, energies and dipole moments of CO+ ions under different external electric fields

F/a.u.	E/Hartree	R_e/Å	μ/Debye
-0.015	-112.760 316 43	1.130 90	2.348 0
-0.010	-112.765 093 44	1.131 06	2.508 8
-0.005	-112.770 184 52	1.131 25	2.667 3
0.0	-112.775 585 88	1.131 78	2.824 2
0.005	-112.781 294 58	1.132 26	2.979 5
0.010	-112.787 308 41	1.133 01	3.133 9
0.015	-112.793 625 39	1.133 82	3.287 2

图3 CO+离子键长、总能量、偶极矩随外加电场的变化

Fig.3 Variation of CO+ ionic bond length, total energy and dipole moment with applied electric field

表4 外加电场对CO分子电荷分布的影响

Table 4 Effect of applied electric field on charge distribution of CO molecules

F/a.u.	C	O
-0.015	0.074	-0.074
-0.010	0.091	-0.091
-0.005	0.107	-0.107
0.0	0.122	-0.122
0.005	0.136	-0.136
0.010	0.149	-0.149
0.015	0.162	-0.162

表5 分子的前线轨道能量与能隙

Table 5 Frontier orbital energy and energy gap

F/a.u.	E_L/eV	E_H/eV	E_G/eV
-0.015	-0.071 83	-0.407 09	0.335 26
-0.010	-0.067 05	-0.401 33	0.334 28
-0.005	-0.063 04	-0.395 73	0.332 69
0.0	-0.059 33	-0.390 31	0.330 98
0.005	-0.055 90	-0.385 06	0.327 22
0.010	-0.052 76	-0.379 98	0.327 22
0.015	-0.049 89	-0.375 08	0.325 19

图4 外加电场下CO分子前线轨道能级的变化

Fig.4 Variation of CO molecular frontier orbit energy under external electric field

表6 离子的前线轨道能量与能隙

Table 6 Frontier orbital energies and energy gaps of ions

Alpha				Beta
F/a.u.	E_L/eV	E_H/eV	E_G/eV	F/a.u.	E_L/eV	E_H/eV	E_G/eV
-0.015	-0.457 96	-0.872 94	11.287 456	-0.015	-0.669 81	-0.872 15	5.503 648
-0.010	-0.455 65	-0.870 00	11.270 32	-0.010	-0.663 98	-0.870 96	5.629 856
-0.005	-0.453 44	-0.867 05	11.250 192	-0.005	-0.658 24	-0.869 87	5.756 336
0.0	-0.451 43	-0.864 06	11.223 536	0.0	-0.652 60	-0.868 76	5.879 552
0.005	-0.449 49	-0.861 05	11.194 432	0.005	-0.647 04	-0.867 77	6.003 856
0.010	-0.447 72	-0.857 99	11.159 344	0.010	-0.641 58	-0.866 78	6.125 44
0.015	-0.446 04	-0.854 90	11.120 992	0.015	-0.636 22	-0.865 87	6.246 48

表7 不同电场下CO分子的红外光谱

Table 7 Vibration frequency and IR electric field intensity of CO molecules under electric fields

F/a.u.	f/cm^-1	IR intensity
-0.015	2 099.28	48.533 6
-0.010	2 088.54	57.668 6
-0.005	2 076.65	67.585 9
0.0	2 063.59	78.304 9
0.005	2 049.34	89.849 8
0.010	2 033.85	102.249 1
0.015	2 017.08	115.536 0

图5 外加电场下CO+离子的(Alpha轨道)前线轨道能级

Fig.5 Frontier orbital energy levels of CO+ ions (Alpha track) under applied electric field

图6 外加电场下CO+离子的(Beta轨道)前线轨道能级

Fig.6 Frontier orbital energy levels of CO+ ions (Beta track) under applied electric field

图7 外电场下CO分子红外光谱

Fig.7 CO molecular infrared spectrum under external electric fields

图8 外电场下CO+离子红外光谱

Fig.8 CO+ ion infrared spectrum under external electric fields

图9 CO分子在外加电场下的势能曲线

Fig.9 Potential energy curves of CO molecular under external electric field

图10 CO+离子在外加电场下的势能曲线

Fig.10 Potential energy curves of CO+ ion under external electric field

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