高分辨偏正拉曼光谱对丙酸酐C=O振动模的拉曼光谱非一致效应研究

doi:10.7503/cjcu20180648

摘要/Abstract

摘要：

根据C=O振动的各向同性和各向异性拉曼光谱和红外光谱特点讨论研究了丙酸酐分子的局部有序排列以及振动耦合机理. 利用三级联共聚焦拉曼光谱仪测定了不同浓度丙酸酐的各向同性与各向异性拉曼光谱图, 分别采集了丙酸酐在四氯化碳和甲醇中的光谱以及不同极性溶剂中的光谱, 具体分析了丙酸酐C=O振动模的浓度效应、溶剂效应以及拉曼光谱非一致效应(NCE). 结果表明, 丙酸酐C=O振动模的NCE效应随着浓度的降低而减小; 随着溶剂极性的减小而增加. 利用密度泛函理论的B3LYP-D3/31-311G(d,p)基组计算了丙酸酐单体和二聚体的几何稳定构型, 用聚集态理论模型解释了丙酸酐分子的NCE效应、浓度效应与溶剂效应. 理论计算结果与实验结果相吻合.

关键词: 丙酸酐, 聚集态理论模型, 拉曼光谱非一致效应, 密度泛函理论

Abstract:

According to the isotropic and anisotropic Raman spectroscopy of C=O vibration and the characteristics of infrared spectroscopy, the local ordered vibration and coupling mechanism of propionic anhydride molecules were studied. The isotropic and anisotropic Raman spectra of different concentrations of propionic anhydride were determined by three-stage confocal Raman microspectroscopy. The spectra of propionic anhydride in carbon tetrachloride and methanol and the spectra in other solvents were collected. Concentration effects, solvent effects, and Raman spectroscopy non-coincidence effects(NCE) of propionic anhydride were analyzed in detail. The results show that the NCE effect of propionic anhydride decreases with decreasing concentration; the NCE value increases with the decreasing of solvent polarity. The geometrically stable configuration of propionic anhydride monomer and dimer was calculated by the density functional theory B3LYP-D3/31-311G(d, p) basis set. The NCE effect, concentration effect and solvent effect of propionic anhydride molecule were explained by the aggregation state theory model. The theoretical calculation results are in agreement with the experimental results.

Key words: Propionic anhydride, Aggregate state theory model, Raman non-coincidence effect(NCE), Density functional theory(DFT)

中图分类号:

O641
O657.3

TrendMD:

刘秋娜, 许文文, 刘茂祝, 王惠钢, 郑旭明. 高分辨偏正拉曼光谱对丙酸酐C=O振动模的拉曼光谱非一致效应研究. 高等学校化学学报, 2019, 40(5): 932.

LIU Qiuna,XU Wenwen,LIU Maozhu,WANG Huigang,ZHENG Xuming. Study on Raman Spectroscopy Non-coincidence Effect of Propionic Anhydride C=O Vibration Mode^†. Chem. J. Chinese Universities, 2019, 40(5): 932.

图/表 11

Fig.1 FTIR(a) and LCM-Raman(b) and Raman spectra of gas phase conditions calculated by DFT theory(c) of propionic anhydride

Fig.2 The most stable geometry of propionic anhydride monomer and dimer in the gas phase calculated at the B3LYP/6-311G(d, p) level (A) Monomer; (B) dimer-top view; (C) dimer-side view.

Table 1 B3LYP/6-311G(d,p) calculation of the frequency of propionic anhydride monomer and dimer, depolarization ratio(D. ratio)

Mode	Calculated				Experimental		Description
	Monomer		Dimer		Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
	Frequency/cm^-1	D. ratio	Frequency^a/cm^-1	D. ratio^b	Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
ν₁	3119	0.74	3132/3132	0.69/0.75			Stre(C16H17)
ν₂	3115	0.75	3123/3123	0.46/0.75			Stre(C1H5)
ν₃	3112	0.70	3132/3132	0.62/0.75			Stre(C1H3)
ν₄	3112	0.68	3108/3108	0.46/0.75			Stre(C16H18)
ν₅	3087	0.62	3103/3102	0.66/0.75			Stre(C13H14)
ν₆	3066	0.73	3076/3076	0.58/0.75			Stre(C2H7)
ν₇	3044	0.06	3048/3047	0.11/0.57			Stre(C13H15)
ν₈	3044	0.01	3045/3045	0.01/0.75			Stre(C16H18)
ν₉	3043	0.20	3043/3043	0.07/0.75			Stre(C16H19)
ν₁₀	3039	0.07	3043/3043	0.75/0.09			Stre(C2H6)
ν₁₁	1871	0.18	1850/1845	0.75/0.04			Stre(O12C11)
ν₁₂	1825	0.19	1822/1813	0.03/0.75	1801vs	1797w	Stre(O9C8)
ν₁₃	1504	0.75	1510/1510	0.75/0.75			Bend(H17C16H19)
ν₁₄	1503	0.75	1504/1504	0.75/0.75	1450vs	1463w	Tore(H4C1C2C8H3C1C2C8)
ν₁₅	1496	0.75	1498/1498	0.75/0.64			Bend(H18C16H17)
ν₁₆	1495	0.75	1495/1495	0.75/0.74			Bend(H4C1H3)
ν₁₇	1461	0.75	1452/1451	0.75/0.75			Bend(H15C13H14)
ν₁₈	1460	0.72	1448/1445	0.75/0.75	1428s	1423w	Bend(H7C2H6)
ν₁₉	1424	0.36	1426/1426	0.31/0.75			Bend(H3C1H5)
ν₂₀	1424	0.73	1419/1419	0.75/0.30			Bend(H18C16H17)
ν₂₁	1382	0.61	1387/1385	0.75/0.75			Tors(H7C2C8O10)
ν₂₂	1379	0.72	1383/1382	0.75/0.53			Tors(H14C13C11O10)
ν₂₃	1293	0.70	1297/1294	0.30/0.75	1318s	1317w	Bend(H14C13H16)
ν₂₄	1283	0.75	1293/1292	0.75/0.75			Bend(H6C2H1,)
ν₂₅	1162	0.50	1158/1157	0.75/0.48			Stre(O10C8)
ν₂₆	1115	0.75	1119/1119	0.75/0.60			Tors(H14C13C11O10)
ν₂₇	1111	0.34	1113/1111	0.59/0.75			Tors(H6C2C8O10)
ν₂₈	1106	0.44	1108/1107	0.75/0.62			TORS(H19C16C13C11)
Mode	Calculated				Experimental		Description
	Monomer		Dimer		Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
	Frequency/cm^-1	D. ratio	Frequency^a/cm^-1	D. ratio^b	Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
ν₂₉	1094	0.07	1101/1091	0.75/0.07			Stre(C1C2)
ν₃₀	1044	0.70	1058/1040	0.75/0.41			Stre(C13C11)
ν₃₁	1025	0.71	1032/1020	0.75/0.47			Stre(C1C2)
ν₃₂	1000	0.40	1003/1002	0.75/0.32			Stre(C16C13)
ν₃₃	905	0.31	911/911	0.75/0.08			Stre(O10C8)
ν₃₄	824	0.61	827/827	0.75/0.31	829vs		Tors(H18C16C13C11)
ν₃₅	818	0.73	822/821	0.75/0.63			Tors(H3C1C2C8) Out(O9C2O10C8)
ν₃₆	775	0.12	777/776	0.06/0.75			Stre(C11C13)
ν₃₇	679	0.61	684/684	0.53/0.75			Bend(O9C8O10)
ν₃₈	642	0.75	636/635	0.75/0.75			Bend(O12C11O10)
ν₃₉	564	0.74	565/560	0.74/0.75			TORS(C1C2C8O10)
ν₄₀	530	0.59	534/529	0.75/0.40			TORS(C16C13C11O10)
ν₄₁	444	0.74	436/436	0.75/0.70			Bend(O12C11O10)
ν₄₂	345	0.29	347/346	0.75/0.22			Bend(C1C2C8)
ν₄₃	296	0.16	304/302	0.75/0.12			Bend(C11O10C8)
ν₄₄	251	0.75	254/249	0.71/0.75			Bend(C1C2O8)
ν₄₅	216	0.58	231/230	0.72/0.75			TORS(H18C16C13C11)
ν₄₆	204	0.67	227/223	0.75/0.71			TORS(H3C1C2C8)
ν₄₇	143	0.52	155/149	0.75/0.58			Bend(C11O10C8)
ν₄₈	100	0.69	137/127	0.75/0.75			TORS(C11O10C8C2)
ν₄₉	57	0.74	108/108	0.75/0.63			TORS(C1C2C8O10)
ν₅₀	46	0.54	106/103	0.75/0.53			TORS(C11O10C8C2)
ν₅₁	19	0.72	89/80	0.75/0.75			TORS(C13C11O10C8)
ν₅₂			72/64	0.74/0.75			Relative rotation
ν₅₃			50/27	0.71/0.75			Relative translation
ν₅₄			25/6.84	0.74/0.73			Relative translation

Table 1 B3LYP/6-311G(d,p) calculation of the frequency of propionic anhydride monomer and dimer, depolarization ratio(D. ratio)

Mode	Calculated				Experimental		Description
	Monomer		Dimer		Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
	Frequency/cm^-1	D. ratio	Frequency^a/cm^-1	D. ratio^b	Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
ν₁	3119	0.74	3132/3132	0.69/0.75			Stre(C16H17)
ν₂	3115	0.75	3123/3123	0.46/0.75			Stre(C1H5)
ν₃	3112	0.70	3132/3132	0.62/0.75			Stre(C1H3)
ν₄	3112	0.68	3108/3108	0.46/0.75			Stre(C16H18)
ν₅	3087	0.62	3103/3102	0.66/0.75			Stre(C13H14)
ν₆	3066	0.73	3076/3076	0.58/0.75			Stre(C2H7)
ν₇	3044	0.06	3048/3047	0.11/0.57			Stre(C13H15)
ν₈	3044	0.01	3045/3045	0.01/0.75			Stre(C16H18)
ν₉	3043	0.20	3043/3043	0.07/0.75			Stre(C16H19)
ν₁₀	3039	0.07	3043/3043	0.75/0.09			Stre(C2H6)
ν₁₁	1871	0.18	1850/1845	0.75/0.04			Stre(O12C11)
ν₁₂	1825	0.19	1822/1813	0.03/0.75	1801vs	1797w	Stre(O9C8)
ν₁₃	1504	0.75	1510/1510	0.75/0.75			Bend(H17C16H19)
ν₁₄	1503	0.75	1504/1504	0.75/0.75	1450vs	1463w	Tore(H4C1C2C8H3C1C2C8)
ν₁₅	1496	0.75	1498/1498	0.75/0.64			Bend(H18C16H17)
ν₁₆	1495	0.75	1495/1495	0.75/0.74			Bend(H4C1H3)
ν₁₇	1461	0.75	1452/1451	0.75/0.75			Bend(H15C13H14)
ν₁₈	1460	0.72	1448/1445	0.75/0.75	1428s	1423w	Bend(H7C2H6)
ν₁₉	1424	0.36	1426/1426	0.31/0.75			Bend(H3C1H5)
ν₂₀	1424	0.73	1419/1419	0.75/0.30			Bend(H18C16H17)
ν₂₁	1382	0.61	1387/1385	0.75/0.75			Tors(H7C2C8O10)
ν₂₂	1379	0.72	1383/1382	0.75/0.53			Tors(H14C13C11O10)
ν₂₃	1293	0.70	1297/1294	0.30/0.75	1318s	1317w	Bend(H14C13H16)
ν₂₄	1283	0.75	1293/1292	0.75/0.75			Bend(H6C2H1,)
ν₂₅	1162	0.50	1158/1157	0.75/0.48			Stre(O10C8)
ν₂₆	1115	0.75	1119/1119	0.75/0.60			Tors(H14C13C11O10)
ν₂₇	1111	0.34	1113/1111	0.59/0.75			Tors(H6C2C8O10)
ν₂₈	1106	0.44	1108/1107	0.75/0.62			TORS(H19C16C13C11)
Mode	Calculated				Experimental		Description
	Monomer		Dimer		Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
	Frequency/cm^-1	D. ratio	Frequency^a/cm^-1	D. ratio^b	Raman shift^c/ cm^-1	IR, $ν ˙ c$ / cm^-1
ν₂₉	1094	0.07	1101/1091	0.75/0.07			Stre(C1C2)
ν₃₀	1044	0.70	1058/1040	0.75/0.41			Stre(C13C11)
ν₃₁	1025	0.71	1032/1020	0.75/0.47			Stre(C1C2)
ν₃₂	1000	0.40	1003/1002	0.75/0.32			Stre(C16C13)
ν₃₃	905	0.31	911/911	0.75/0.08			Stre(O10C8)
ν₃₄	824	0.61	827/827	0.75/0.31	829vs		Tors(H18C16C13C11)
ν₃₅	818	0.73	822/821	0.75/0.63			Tors(H3C1C2C8) Out(O9C2O10C8)
ν₃₆	775	0.12	777/776	0.06/0.75			Stre(C11C13)
ν₃₇	679	0.61	684/684	0.53/0.75			Bend(O9C8O10)
ν₃₈	642	0.75	636/635	0.75/0.75			Bend(O12C11O10)
ν₃₉	564	0.74	565/560	0.74/0.75			TORS(C1C2C8O10)
ν₄₀	530	0.59	534/529	0.75/0.40			TORS(C16C13C11O10)
ν₄₁	444	0.74	436/436	0.75/0.70			Bend(O12C11O10)
ν₄₂	345	0.29	347/346	0.75/0.22			Bend(C1C2C8)
ν₄₃	296	0.16	304/302	0.75/0.12			Bend(C11O10C8)
ν₄₄	251	0.75	254/249	0.71/0.75			Bend(C1C2O8)
ν₄₅	216	0.58	231/230	0.72/0.75			TORS(H18C16C13C11)
ν₄₆	204	0.67	227/223	0.75/0.71			TORS(H3C1C2C8)
ν₄₇	143	0.52	155/149	0.75/0.58			Bend(C11O10C8)
ν₄₈	100	0.69	137/127	0.75/0.75			TORS(C11O10C8C2)
ν₄₉	57	0.74	108/108	0.75/0.63			TORS(C1C2C8O10)
ν₅₀	46	0.54	106/103	0.75/0.53			TORS(C11O10C8C2)
ν₅₁	19	0.72	89/80	0.75/0.75			TORS(C13C11O10C8)
ν₅₂			72/64	0.74/0.75			Relative rotation
ν₅₃			50/27	0.71/0.75			Relative translation
ν₅₄			25/6.84	0.74/0.73			Relative translation

Fig.3 Isotropic and anisotropic partial Raman spectra of propionic anhydride with different volume fractions in CCl4 in a spectral region of 1770—1850 cm-1Xm is volume fraction of propionic anhydride.

Fig.4 Isotropic and anisotropic vibrational frequencies of C=O vibration at different volume fraction of propionic anhydride(in CCl4)

Fig.5 Relationship between ΔνNCE of C=O vibration mode and volume fraction of propionic anhydride in CCl4

Fig.6 Isotropic and anisotropic partial Raman spectra of propionic anhydride with diffe-rent volume fractions in CH3OH in a spectral region of 1775—1845 cm-1

Fig.7 Isotropic and anisotropic vibrational frequencies of C=O vibration at different volume fraction of propionic anhydride(in CH3OH)

Fig.8 Relationship between ΔνNCE of C=O vibration mode and volume fraction of propionic anhydride in CH3OH

Fig.9 Isotropic and anisotropic partial Raman spectroscopy of C=O in propionic anhydride with a volume fraction of 0.4 in cyclohexane, CCl4, tetrahydrofuran(THF), ethanol and methanol, respectively

Fig.10 Variation of ΔνNCE of C=O vibration mode of propionic anhydride versus solvent polarity

参考文献 31

[1]	Urban M., Hobza P., Theoreticachimica Acta., 1975, 36(3), 207—214
[2]	Golding J., Macfarlane D. R., Forsyth M., Retrospective Collection,1998, 25, 146—146
[3]	Pescitelli G., Bari L. D., Berova N., Chemical Society Reviews,2014, 43(15), 5211—5233
[4]	Braga D., Grepioni F., Accounts of Chemical Research,2000, 33(9), 601—608
[5]	Wolters L. P., Schyman P., Pavan M. J., Jorgensen W. L., Bickelhaupt F. M., Kozuch S., Wiley Interdisciplinary Reviews Computational Molecular Science,2014, 4(6), 523—540
[6]	Zordan F., Brammer L., Sherwood P., Journal of America Chemistry Society,2005, 127(16), 5979—5989
[7]	Pihko P. M., Angew. Chem., 2004, 43(6), 2062—2064
[8]	Kosmider L., Sobczak A., Fik M., Knysak J., Zaciera M., Kurek J., Goniewicz L. M., Nicotine & Tobacco Research,2014, 16(10), 1319—1326
[9]	Bekki K., Uchiyama S., Ohta K., Inaba Y., Nakagome H., Kunugita N., International Journal of Environmental Research and Public Health,2014, 11(11), 11192—11200
[10]	Xu Y., Hua E., Chem. J. Chinese Universities,2018, 39(10), 1954—1960
	(徐宇, 花儿. 高等学校化学学报,2018, 39(10), 1954—1960)
[11]	Kasyanenko V. M., Keiffer P., Rubtsov I. V., Journal of Chemical Physics,2012, 136(14), 144—503
[12]	Musso M., Torii H., Giorgini M. G., Döge G., Journal of Chemical Physics,1999, 110(20), 10076—10085
[13]	Fini G., Mirone P., Journal of the Chemical Society-Faraday Transactions Ⅱ,1974, 70, 1776—1782
[14]	Giorgini M. G., Musso M., Asenbaum A., Molecular Physics,2000, 98(12), 783—791
[15]	Musso M., Giorgini M. G., Asenbaum G. D., Molecular Physics,1997, 92(1), 97—104
[16]	Upadhyay G., Devi T. G., Singh R. K., Singh A., Alapati P. R., Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2013, 109(4), 239—246
[17]	Giorgini M. G., Arcioni A., Polizzi C., Musso M., Ottaviani P., Journal of Chemical Physics,2004, 120(10), 4969—4979
[18]	Ojha A. K., Srivastava S. K., Schlücker S., Kiefer W., Asthana B. P., Singh R. K., Journal of Raman Spectroscopy,2010, 38(12), 1656—1664
[19]	Torii M. H., Musso M. G., Giorgini G. D., Molecular Physics,1998, 94(5), 821—828
[20]	Logan D. E., Chemical Physics, 1986, 103(2), 215—225
[21]	Giorgini M. G., Torii H., Musso M., Physical Chemistry Chemical Physics,2010, 12(1), 92—183
[22]	Pádua A. A. H., Gomes M. F. C., Lopes J. N. A. C., Accounts of Chemical Research,2007, 40(11), 1087—1096
[23]	Wu F. Q., Wang H. G., Zheng X. M., Journal of Raman Spectroscopy,2015, 46(6), 591—596
[24]	Xu W. W., Wu F. Q.,, Zhao Y. Y., Zhou R., Wang H. G., Zheng X. M., Ni B., Sci. Rep.,2017, 7, 43835
[25]	Lu T., Chen F., Journal of Computational Chemistry,2012, 33(5), 580—592
[26]	Keresztury G., Holly S., Besenyei G., Varga J., Wang A., Durig J. R., Spectrochimica Acta Part A: Molecular Spectroscopy,1993, 49(13/14), 2007—2026
[27]	Chen L., Yang X. G., Zheng X. M., Spectroscopy and Spectral Analysis,2013, 33(12), 3244—3248
	(陈林, 杨晓刚, 郑旭明. 光谱学与光谱分析,2013, 33(12), 3244—3248)
[28]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery Jr. J. A., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmain G., Rega N., Petersson G. A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Ayala P. Y., Morokuma K., Voth G. A., Salvador P., Dannenberg J. J., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain C. M., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cui Q., Baboul A. G., Clifford S., Cioslowski J., Stefanov B. B., Lui G., Liashenko A., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., Peng C. Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 03, Revision C.02, Gaussian Inc., Pittsburgh, 2003
[29]	Meirovitch H., Vasquez M., Scheraga H. A., Biopolymers,2010, 27(8), 1189—1204
[30]	Tanabe K., Tsuzuki S., Spectrochimica Acta Part A: Molecular Spectroscopy,1986, 42(10), 1197—1199
[31]	Logan D. E., Chemical Physics, 1989, 131(2), 199—207