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摘要

利用密度泛函理论B3LYP的方法, 在6-311++G(d, p)基组水平上沿二面角 ϕ ₁(C9N1C2C5)和 ϕ ₂(C16N1C9C12)构成的二维坐标下扫描了–180°—180°范围内构象异构化势能面, 甄别出12种三乙胺基态异构体. 进一步辅以二阶微扰理论MP2的方法, 在相同基组水平下计算与优化6种能量较低的构象异构体的结构与能量. 结果表明具有C ₃对称性的G1与G1'是最稳定构象, 并识别出两种具有新的甲基取向的G4与G4'构象异构体. 另外, 通过G1—G4红外光谱与振动模式的比较, 分析了它们之间的相似性与差异性. G1—G4的红外谱线显示在0—1600 cm ^–1范围内的强度较弱, 而在2800—3300 cm ^–1范围内的强度较强, 标定出伞状振动与C—H伸缩振动等特征振动模, 不同构象所引起的红外谱峰的平均移动量小于20 cm ^–1.

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Abstract

Based on the method of density functional theory B3LYP with a 6-311++G(d, p) basis set, the potential energy surface of conformational isomerization along the two-dimensional coordinates formed by the dihedral angles ϕ ₁(C9N1C2C5) and ϕ ₂(C16N1C9C12) in a range of –180°–180° is investigated. And 12 ground state conformers of triethylamine are identified. Furthermore,with the second-order Moller-Plesset perturbation theory MP2 on the same basis set level, the structures of six lower-energy conformers are optimized and their energy values are estimated. The results show that G1 and G1' with C ₃symmetry are the most stable conformers and G4 and G4' with new methyl orientations are identified. In addition, some vibrational modes in the infrared spectra of G1–G4 are assigned and discussed. The infrared spectra of G1–G4 show that the intensity is weak in a range of 0–1600 cm ^–1, while the intensity is strong in a range of 2800–3300 cm ^–1. The characteristic vibration modes such as umbrella vibration and CH stretching vibration are assigned. The average shift of the corresponding infrared peaks on different conformations is estimated at less than 20 cm ^–1.

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作者及机构信息

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通信作者:龙金友,longjy@wipm.ac.cn; 张嵩,zhangsong@wipm.ac.cn

基金项目:科技部重点研发计划(批准号: 2019YFA0307700)和国家自然科学基金项目(批准号: 11974381, 21873114, 11774385, 21773299, 12074389)资助的课题.

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Corresponding author:Long Jin-You,longjy@wipm.ac.cn; Zhang Song,zhangsong@wipm.ac.cn

Funds:Project supported by the National Key Research and Development Program of China (Grant No. 2019YFA0307700) and the National Natural Science Foundation of China (Grant Nos. 11974381, 21873114, 11774385, 21773299, 12074389).

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参考文献

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施引文献

下载: 全尺寸图片幻灯片

Conformers	ϕ₁/(°)	ϕ₂/(°)	ϕ₃/(°)	Energy/Hartree	RelativeE/meV
G1 (GGG)	155.42	155.60	155.64	–292.501669	0
G1' (G'G'G')	77.67	77.63	77.63	–292.501620	1.33
G2 (TG'G')	–66.62	76.02	63.21	–292.500061	43.76
G3 (TGG)	–64.76	165.17	151.59	–292.500061	43.76
G4 (GG'G'')	162.85	67.24	115.28	–292.499824	50.21
G4' (G'G''G)	67.24	115.26	162.86	–292.499824	50.21
G5 (G'GT)	–167.71	–60.28	65.25	–292.499826	50.15
G6 (GGT)	–75.99	–63.21	66.63	–292.500061	43.76
G7 (G'G'T)	–165.17	–151.59	64.75	–292.500061	43.76
G8 (G'TG)	60.28	–65.24	167.73	–292.499826	50.15
G9 (GTG)	151.58	–64.74	165.19	–292.500061	43.76
G10 (TG'T)	56.64	–156.48	76.67	–292.497311	118.59

下载: 导出CSV

Conformers	ϕ₁/(°)	ϕ₂/(°)	ϕ₃/(°)	Energy/Hartree	RelativeE/meV
G1 (GGG)	157.62	157.63	157.63	–291.559737	0
G1' (G'G'G')	79.53	79.53	79.53	–291.559737	0
G2 (TG'G')	–66.91	75.27	57.80	–291.558559	32.06
G3 (TGG)	–59.62	175.87	158.42	–291.558563	31.95
G4 (GG'G'')	166.11	67.66	117.32	–291.558516	33.23
G4' (G'G''G)	67.74	117.11	166.19	–291.558517	33.20

下载: 导出CSV

Modes	Frequency /cm^–1				Infrared /(arb. units)
Modes	G1	G2	G3	G4	G1	G2	G3	G4
ν1	87.22	55.02	55.10	50.35	0.1532	0.0639	0.0639	0.0004
ν2	90.98	87.43	87.41	96.49	0.1978	0.1857	0.1857	0.0238
ν3	95.03	109.27	109.28	140.35	0.1084	0.2932	0.2933	0.7795
ν4	188.06	178.51	178.54	178.16	1.1011	2.0829	2.0830	1.1365
ν5	208.61	203.62	203.58	205.94	0.0793	0.0717	0.0724	0.0393
ν6	214.02	224.68	224.73	223.87	0.0468	0.0690	0.0687	0.1212
ν7	294.38	268.43	268.36	256.33	1.0986	0.3758	0.3757	0.1000
ν8	304.06	290.93	290.98	328.65	0.3330	1.0227	1.0225	1.6826
ν9	305.06	331.61	331.61	332.28	0.3301	0.6897	0.6908	0.3791
ν10	427.73	407.68	407.74	390.84	3.0184	1.9295	1.9286	1.8981
ν11	465.12	465.26	465.28	449.38	1.9245	2.3956	2.3948	1.6278
ν12	466.51	519.32	519.35	495.27	1.9272	6.0474	6.0464	0.2229
ν13	732.52	721.09	721.08	734.07	12.9402	9.4813	9.4797	10.9942
ν14	786.67	769.53	769.53	763.17	3.8307	4.3371	4.3412	6.1536
ν15	787.30	788.70	788.71	790.73	3.8921	2.6364	2.6346	1.2979
ν16	797.88	799.48	799.50	799.56	0.0602	1.6382	1.6374	1.5619
ν17	907.63	886.81	886.80	911.00	1.2513	1.6792	1.6806	1.3188
ν18	907.82	906.38	906.37	911.59	1.2450	1.3085	1.3102	0.5529
ν19	1002.59	983.42	983.41	1003.17	6.7677	11.0738	11.0739	5.7366
ν20	1059.24	1035.02	1035.00	1056.02	29.6466	8.2727	8.2697	18.7155
ν21	1059.73	1059.50	1059.46	1058.63	30.0288	30.8396	31.1034	16.0090
ν22	1065.72	1062.07	1062.06	1069.23	3.2100	8.4580	8.2166	30.8172
ν23	1078.10	1078.78	1078.77	1076.49	8.5384	3.6151	3.6028	1.3100
ν24	1078.68	1090.02	1090.04	1102.40	8.3190	28.7911	28.7831	8.1051
ν25	1145.20	1130.09	1130.09	1132.97	12.0682	10.1819	10.1824	19.8481
ν26	1208.09	1204.99	1204.96	1210.21	23.0883	18.4553	18.4412	17.6571
ν27	1208.58	1213.11	1213.11	1213.26	23.1735	25.1079	25.1196	35.4460
ν28	1295.98	1286.87	1286.86	1275.96	6.1543	5.5069	5.5346	4.4355
ν29	1299.90	1291.74	1291.73	1307.05	19.8870	19.0478	19.0085	20.9498
ν30	1301.08	1338.30	1338.29	1319.27	19.5949	13.3278	13.3106	1.2005
ν31	1368.21	1352.09	1352.09	1354.63	1.9917	11.3690	11.3924	37.8361
ν32	1369.16	1366.65	1366.64	1357.26	1.2772	3.0836	3.0821	5.3537
ν33	1377.64	1375.36	1375.35	1377.69	0.3191	3.9451	3.9459	0.5963
ν34	1388.04	1377.00	1377.00	1381.06	17.8509	14.4179	14.4269	19.6423
ν35	1388.15	1386.56	1386.55	1382.64	18.3740	20.6580	20.6282	12.8529
ν36	1388.87	1390.27	1390.26	1404.98	19.7944	15.6998	15.6974	5.4524
ν37	1457.17	1452.04	1452.05	1453.70	2.7473	4.8488	4.8565	5.2712
ν38	1457.42	1458.81	1458.81	1455.34	1.6935	4.5549	4.5301	0.3420
ν39	1457.69	1461.08	1461.08	1458.89	2.2572	2.7707	2.7867	3.6730
ν40	1462.71	1465.68	1465.67	1462.41	1.8527	2.0538	2.0584	4.0415
ν41	1470.31	1469.26	1469.25	1465.41	1.2048	3.4122	3.4014	0.0857
ν42	1470.92	1470.19	1470.18	1473.12	1.5336	1.3596	1.3783	3.1465
ν43	1480.41	1477.89	1477.88	1478.47	7.1590	2.9233	2.9249	1.5156
ν44	1481.40	1480.62	1480.60	1484.66	7.0152	14.8916	14.8851	10.1121
ν45	1485.83	1490.87	1490.86	1487.68	12.4306	1.4478	1.4478	14.3785
ν46	2840.18	2846.52	2846.55	2823.87	23.2447	36.5331	36.7500	30.6694
ν47	2840.74	2855.55	2855.62	2833.67	23.3082	133.4917	133.2390	190.3336
ν48	2852.73	2964.14	2964.10	2931.98	238.2268	28.9250	28.9420	52.7107
ν49	2966.71	2965.86	2965.83	2961.43	29.7433	22.5935	22.5842	24.4676
ν50	2967.27	2967.80	2967.77	2962.15	29.7303	26.9332	26.9495	32.0017
ν51	2967.73	2969.71	2969.69	2966.69	20.4277	26.6680	26.6499	55.0959
ν52	3005.55	2985.78	2985.82	2967.51	12.9188	19.0174	18.9607	9.9999
ν53	3006.00	2999.96	2999.91	2982.63	12.0858	16.2484	16.2880	1.3433
ν54	3009.33	3003.92	3003.90	2993.29	0.0669	7.0967	7.1223	29.3355
ν55	3025.88	3022.39	3022.35	3025.08	9.0331	39.4849	39.4879	51.7362
ν56	3028.87	3026.72	3026.71	3026.92	48.6932	15.0249	15.0950	24.4990
ν57	3029.12	3029.64	3029.64	3028.60	44.4949	61.7552	61.8929	54.1919
ν58	3037.74	3031.73	3031.72	3036.45	53.6899	42.2463	42.0251	3.3194
ν59	3039.70	3037.26	3037.24	3037.37	45.2729	52.3351	52.2987	69.7071
ν60	3040.26	3040.20	3040.20	3041.40	46.0316	44.4987	44.5093	31.7214

下载: 导出CSV

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