Density functional theory calculation of spectrum and excitation properties of mer-Alq3

Jie Peng; Si-Jie Zhang; Ke Wang; Martin Dove

doi:10.7498/aps.69.20191453

Journals >Acta Physica Sinica >Volume 69 >Issue 2 >Page 023101-1 > Article

Acta Physica Sinica
Vol. 69, Issue 2, 023101-1 (2020)

Density functional theory calculation of spectrum and excitation properties of mer-Alq₃

Jie Peng, Si-Jie Zhang^*, Ke Wang, and Martin Dove

DOI: 10.7498/aps.69.20191453 Cite this Article

Jie Peng, Si-Jie Zhang, Ke Wang, Martin Dove. Density functional theory calculation of spectrum and excitation properties of mer-Alq₃[J]. Acta Physica Sinica, 2020, 69(2): 023101-1 Copy Citation Text

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Structure of the mer-Alq3 molecule.mer-Alq3的分子结构

Fig. 1. Structure of the mer-Alq₃ molecule. mer-Alq₃的分子结构

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Infrared absorption spectrum of mer-Alq3.mer-Alq3分子的红外光谱

Fig. 2. Infrared absorption spectrum of mer-Alq₃. mer-Alq₃分子的红外光谱

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Fig. 3. Raman spectrum of mer-Alq₃. mer-Alq₃的拉曼光谱

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Fig. 4. Frontier molecular orbits of mer-Alq₃: (a) HOMO-2 distribution; (b) HOMO-1 distribution; (c) HOMO distribution; (d) LUMO distribution; (e) LUMO+1 distribution; (f) LUMO+2 distribution. mer-Alq₃前线分子轨道分布图　(a) HOMO-2轨道分布图; (b) HOMO-1轨道分布图; (c) HOMO轨道分布图; (d) LUMO轨道分布图; (e) LUMO+1轨道分布图; (f) LUMO+2轨道分布图

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Fig. 5. UV-Vis absorption spectrum of mer-Alq₃. mer-Alq₃分子的紫外-可见吸收光谱

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Fig. 6. Electron-hole, Chole-Cele and S_r distributions of mer-Alq₃ respectively: (a)−(c) Electron-hole, Chole-Cele,S_r distribution at S2 state geometry; (d)−(f) Electron-hole, Chole-Cele,S_r distribution at S4 state geometry; (g)−(i) Electron-hole, Chole-Cele,S_r distribution at S11 state geometry; (j)−(l) Electron-hole, Chole-Cele,S_r distribution at S14 state geometry mer-Alq₃的空穴-电子、Chole-Cele、S_r示意图　(a)−(c) S2的空穴-电子, Chole-Cele,S_r图; (d)−(f) S4的空穴-电子, Chole-Cele,S_r图; (g)−(i) S11的空穴-电子, Chole-Cele,S_r图; (j)−(l) S14的空穴-电子, Chole-Cele,S_r图

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Bond	B3LYP/6-31G*/Å	Experimental results/Å^[21]
Al-Na	2.08377	2.0502
Al-Nb	2.12565	2.0872
Al-Nc	2.06431	2.0172
Al-Oa	1.85545	1.8502
Al-Ob	1.88106	1.8602
Al-Oc	1.88398	1.8572

Table 1.

Bond lengths of the mer-Alq₃.

mer-Alq₃分子的键长

V_experiment/cm^–1	V_theory/cm^–1	Vibration analysis	V_experiment/cm^–1	V_theory/cm^–1	Vibration analysis
398	408	分子骨架扭曲变形	1228	1268	C—N伸缩振动, C—H平面摇摆振动, 剪式振动
416	422	分子骨架扭曲变形, 环1环2环5 环6上C—H平面摇摆振动, 环3环4上C—H扭曲振动	1280	1334	C—O, C—C伸缩振动, C—H平面摇摆振动
457	470	C—H扭曲振动	1328	1376	C—H平面摇摆振动, 剪式振动
548	554	Al-O50伸缩振动, 环1环2呼吸振动	1383	1422	C—C伸缩振动, C—H平面摇摆振动
642	662	Al-O50伸缩振动, C—H扭曲振动	1424	1438	C—N、C—C伸缩振动, C—H 平面摇摆振动, 剪式振动
746	768	Al-O面外弯曲振动, 环3环4呼吸振动	1468	1512	C—N伸缩振动, C—C伸缩振动, C—H平面摇摆振动
787	796	C—H扭曲振动	1499	1550	C—C伸缩振动, C—H平面摇摆振动
803	820	苯环和吡啶环变形振动	1579	1636	C—N伸缩振动, C—C伸缩振动, C—H平面摇摆振动, 剪式振动
823	836	C—H面外摇摆振动	1606	1658	C—N伸缩振动, C—C伸缩振动, C—H平面摇摆振动, 剪式振动
1114	1140	C—H剪式振动	3039	3202	苯环上C—H伸缩振动

Table 2.

Identification of partial vibration modes of mer-Alq₃.

mer-Alq₃分子中部分振动模式指认

V_experiment/cm^–1	V_theory/cm^–1	Vibration analysis
507	508	Al—O扭曲振动, 苯环和吡啶环变形振动
529	530	Al—O伸缩振动, 苯环和吡啶环呼吸振动
545	554	Al—O伸缩振动, 苯环和吡啶环呼吸振动
581	586	Al—O扭曲振动, 苯环和吡啶环变形振动
760	768	Al—O伸缩振动, 苯环和吡啶环呼吸振动
1062	1086	C—H平面摇摆振动, 剪式振动
1177	1172	C—H平面摇摆振动, 剪式振动
1393	1422	C—O, C—C伸缩振动, C—H平面摇摆振动, 剪式振动
—	1438	C—N、C—C伸缩振动, C—H平面摇摆振动, 剪式振动
1593	1638	C—C伸缩振动, C—H平面摇摆振动, 剪式振动
—	3216	C—H伸缩振动

Table 3.

Identification of partial vibration modes of mer-Alq₃.

mer-Alq₃分子中部分振动模式指认

分子轨道	能级	Al		a			b			c
分子轨道	能级	Al	O	苯	吡啶	O	苯	吡啶	O	苯	吡啶
H-2	–0.19584	1.51	0.16	0.85	0.93	20.36	64.59	19.94	0.24	0.74	1.15
H-1	–0.19204	1.57	2.05	8.50	2.56	0.36	1.18	1.17	17.19	58.30	17.72
H	–0.18397	1.47	19.25	57.52	17.84	0.36	0.20	0.24	3.58	7.26	2.42
L	–0.06363	1.60	0.06	0.18	0.91	1.66	25.28	64.81	0.29	4.55	12.18
L+1	–0.05496	1.36	0.62	8.41	20.90	0.24	3.24	7.25	1.33	19.64	47.98
L+2	–0.05218	1.28	1.72	21.57	56.03	0.54	1.83	5.13	0.81	6.32	16.59

Table 4.

Frontier molecular orbital energy levels (in arb.units) and distribution (in %) of mer-Alq₃.

mer-Alq₃的前线分子轨道能级(单位: arb.units)及分布(单位: %)

Excited state	λ/nm	f	Transition nature (contribution > 10%)	Transition energy/eV
2	427.15	0.0672	119→121 (45.9956%); 119→122 (23.0683%); 118→120 (21.1263%)	2.9026
4	417.31	0.0425	117→120 (88.1022%)	2.9710
11	304.03	0.0151	119→124 (38.2445%); 119→125 (23.0208%)	4.0781
12	302.87	0.0214	117→123 (66.2078%); 114→120 (20.1638%)	4.0937

Table 5.

The analysis of electron excitation of mer-Alq₃.

mer-Alq₃分子的电子激发分析表

	D/Å	S_r/arb.units	H/Å	t/Å
S0 → S2	0.18	0.61	3.57	0.12
S0 → S4	0.99	0.59	2.95	0.41
S0 → S11	0.88	0.79	3.84	–1.38
S0 → S14	0.68	0.43	3.47	2.00

Table 6.

Excited state parameters of mer-Alq₃.

mer-Alq₃分子的激发态参数

Jie Peng, Si-Jie Zhang, Ke Wang, Martin Dove. Density functional theory calculation of spectrum and excitation properties of mer-Alq₃[J]. Acta Physica Sinica, 2020, 69(2): 023101-1

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