2-硝基萘激发态衰减动力学和光解通道的从头计算研究

doi:10.7503/cjcu20170768

摘要/Abstract

摘要：

采用密度泛函理论(DFT)和完全活化空间自洽场理论(CASSCF) 计算方法, 在CASSCF(10,10)/6-31G(d)//CASPT2(10,10)/Aug-cc-PVDZ计算水平下, 研究了2-硝基萘(2NN) S₁(ππ^*)激发态的衰减动力学. 获得了2NN及其亚硝酸酯异构体(ISO)的基态、低能激发态和势能面交叉点的优化结构和能量, 以及异构化反应的过渡态结构和能垒; 给出了S₀, T₁和S₁态时ISO沿N—O键的势能曲线; 描绘了激发态衰变路径图. 结果表明, 被激发至S₁(ππ^*)激发态后, 2NN经S₁T₃, S₁T₂交叉点发生S₁®T₃, S₁®T₂系间窜越过程再经T₂T₁锥形交叉点发生T₂®T₁内转换过程, 最后无辐射衰减到T₁态. 具体衰减路径可以描述为 S_1-FC-2NN® S₁T_3-MIN-2NN或S₁T_2-MIN-2NN®T_3-MIN-2NN或T_2-MIN-2NN® T₂T_1-MIN-2NN®T_1-MIN-2NN. 该条路径能垒较小, T₁态瞬态物种形成效率较高, 为2NN激发态衰变动力学中最重要的无辐射衰变通道. 在S₀, T₁和S₁态势能面上, 2NN®ISO异构化反应的能垒高, 跃迁概率十分低下, 难以形成芳氧自由基(Ar $O ·$ ), 2NN紫外光解离效率很低.

关键词: 2-硝基萘, 完全活化空间自洽谈场理论, 衰减动力学, 异构化反应, 光解离

Abstract:

Density functional theory(DFT) and complete active space self-consistent field(CASSCF) calculation methods, combination with the level of activation space(10,10), and basis set 6-31G(d) were used to obtain structures information of ground state, excited states, intersections and transition states for 2-nitronaphthalene(2NN) and its nitrous acid ester isomer(ISO). Multi-configurational second-order perturbation(CASPT2) method with basis set Aug-cc-PVDZ was adopted in calculating the energy of all the given structures and the Frank-Condon areas. At the same time, the potential energy surface scans along N—O bond were carried out to determine the feasibility of the dissociation for isomers. Finally, the overall picture of decay dynamics for 2NN after being excited to S_1-FC(ππ^*) was presented based on those calculation results. The results show that the nonradiative decay pathway to T₁ state of 2NN originates from S_1-FC(ππ^*), undergoes intersystem crossing and internal conversion through curve-crossing points of S₁T₃, S₁T₂ and T₂T₁. Thus the efficient decay channel can be: S_1-FC-2NN®S₁T_3-MIN-2NN or S₁T_2-MIN-2NN®T_3-MIN-2NN or T_2-MIN-2NN®T₂T_1-MIN-2NN®T_1-MIN-2NN. This pathway is the most important nonradiative decay channel for excited state decay dynamics of 2NN due to the small energy barrier and high efficiency of forming transient species of T₁ state. In addition, calculation results on the potential energy surface suggest that isomerization reactions from 2NN to ISO need to overcome big energy barriers in S₀, T₁ and S₁ states, respectively, which results in the pretty low efficiency of Ar $O ·$ radicals.

Key words: 2-Nitronaphthalene, Complete active space self-consistent field(CASSCF), Decay dynamic, Isomerization, Photodissociation

中图分类号:

O641

TrendMD:

杨梦, 张腾烁, 郑旭明, 薛佳丹. 2-硝基萘激发态衰减动力学和光解通道的从头计算研究. 高等学校化学学报, 2018, 39(8): 1734.

YANG Meng, ZHANG Tengshuo, ZHENG Xuming, XUE Jiadan. Study on the Decay Dynamic of Excited State and Photodissociation Channel for 2-Nitronaphthalene^†. Chem. J. Chinese Universities, 2018, 39(8): 1734.

图/表 7

Fig.1 Front view of the optimized structures for stationary, transition states and curve-crossing points of 2NN and ISOSelected bonds distances are in nm.

Table 1 CASPT2(10,10)/6-31G(d)//CASPT2(10,10)/Aug-cc-PVDZ calculated excitation energies of the low-lying electronic states and curve-crossings of 2NN and ISO

System	Species	Character	ΔE/(kJ·mol^-1)	System	Species	Character	ΔE/(kJ·mol^-1)
2NN	S_0-MIN-2NN		0		T $S (S 0, 2 NN ? ISO)$		270.7
	S_1-FC-2NN	ππ^*	411.7		T $S (T 1, 2 NN ? M)$		390.4
	T_1-FC-2NN	ππ^*	347.3		T_1-MIN-M		370.3
	T_2-FC-2NN	π_NOπ^*	375.7		T $S (T 1, M ? ISO)$		392.0
	T_3-FC-2NN	ππ^*	439.7		T $S (S 1, 2 NN ? M)$		484.5
	S_1-MIN-2NN	ππ^*	369.0		S_1-MIN-M		448.1
	T_3-MIN-2NN	ππ^*	410.5		T $S (S 1, M ? ISO)$		468.2
	T_2-MIN-2NN	n_NOπ^+ππ^	315.9	ISO	$S 0 ? MIN ? ISO$		40.2
	T_1-MIN-2NN	π_NOπ^*	290.8		S_1-FC-ISO	ππ^*	470.7
	S₁ $T 3 ? MIN ? 2 NN$	ππ^/ππ^	405.1(389.5/420.9)^a		T_1-FC-ISO	ππ^*	370.7
	S₁ $T 2 ? MIN ? 2 NN$	ππ^/ππ^	396.6(397.9/395.4)^a		S_1-MIN-ISO	ππ^*	449.8
	T₂ $T 1 ? MIN ? 2 NN$	π_NOπ^/π_NOπ^	326.4(329.7/323.0)^a		T_1-MIN-ISO	ππ^*	306.3

Table 1 CASPT2(10,10)/6-31G(d)//CASPT2(10,10)/Aug-cc-PVDZ calculated excitation energies of the low-lying electronic states and curve-crossings of 2NN and ISO

System	Species	Character	ΔE/(kJ·mol^-1)	System	Species	Character	ΔE/(kJ·mol^-1)
2NN	S_0-MIN-2NN		0		T $S (S 0, 2 NN ? ISO)$		270.7
	S_1-FC-2NN	ππ^*	411.7		T $S (T 1, 2 NN ? M)$		390.4
	T_1-FC-2NN	ππ^*	347.3		T_1-MIN-M		370.3
	T_2-FC-2NN	π_NOπ^*	375.7		T $S (T 1, M ? ISO)$		392.0
	T_3-FC-2NN	ππ^*	439.7		T $S (S 1, 2 NN ? M)$		484.5
	S_1-MIN-2NN	ππ^*	369.0		S_1-MIN-M		448.1
	T_3-MIN-2NN	ππ^*	410.5		T $S (S 1, M ? ISO)$		468.2
	T_2-MIN-2NN	n_NOπ^+ππ^	315.9	ISO	$S 0 ? MIN ? ISO$		40.2
	T_1-MIN-2NN	π_NOπ^*	290.8		S_1-FC-ISO	ππ^*	470.7
	S₁ $T 3 ? MIN ? 2 NN$	ππ^/ππ^	405.1(389.5/420.9)^a		T_1-FC-ISO	ππ^*	370.7
	S₁ $T 2 ? MIN ? 2 NN$	ππ^/ππ^	396.6(397.9/395.4)^a		S_1-MIN-ISO	ππ^*	449.8
	T₂ $T 1 ? MIN ? 2 NN$	π_NOπ^/π_NOπ^	326.4(329.7/323.0)^a		T_1-MIN-ISO	ππ^*	306.3

Fig.2 Orbital configurations obtained by theoritical calculation

Table 2 CASPT2(10,10) calculated one electron density associated the curve-crossing points of 2NN

2NN	Electron density
2NN	41 (π_H-4)	42 (π_NOH-3)	43 (π_H-2)	44 (π_H-1)	45 (π_H)	45 (π_H+n_H)	46 ( $π L *$ )	46 ( $π NOL *$ )	47 ( $π L + 1 *$ )	48 ( $π L + 2 *$ )	49 ( $π L + 3 *$ )	50 ( $π L + 4 *$ )
S₁T_3-MIN-2NN	1.87	1.93	1.90	1.53	1.36	—	0.50	—	0.06	0.10	0.12	0.64
	1.87	1.94	1.92	1.13	1.74	—	0.87	—	0.05	0.12	0.09	0.27
S₁T_2-MIN-2NN	1.87	1.93	1.90	1.52	1.36	—	0.644	—	0.06	0.10	0.12	0.50
	1.88	1.94	1.89	1.53	1.37	—	0.51	—	0.10	0.05	0.12	0.62
T₂T_1-MIN-2NN	1.99	1.00	1.95	1.99	—	1.93	—	1.00	0.01	0.08	0.05	0.00
	1.99	1.00	1.95	1.99	1.93	—	—	1.00	0.00	0.08	0.05	0.01

Table 2 CASPT2(10,10) calculated one electron density associated the curve-crossing points of 2NN

2NN	Electron density
2NN	41 (π_H-4)	42 (π_NOH-3)	43 (π_H-2)	44 (π_H-1)	45 (π_H)	45 (π_H+n_H)	46 ( $π L *$ )	46 ( $π NOL *$ )	47 ( $π L + 1 *$ )	48 ( $π L + 2 *$ )	49 ( $π L + 3 *$ )	50 ( $π L + 4 *$ )
S₁T_3-MIN-2NN	1.87	1.93	1.90	1.53	1.36	—	0.50	—	0.06	0.10	0.12	0.64
	1.87	1.94	1.92	1.13	1.74	—	0.87	—	0.05	0.12	0.09	0.27
S₁T_2-MIN-2NN	1.87	1.93	1.90	1.52	1.36	—	0.644	—	0.06	0.10	0.12	0.50
	1.88	1.94	1.89	1.53	1.37	—	0.51	—	0.10	0.05	0.12	0.62
T₂T_1-MIN-2NN	1.99	1.00	1.95	1.99	—	1.93	—	1.00	0.01	0.08	0.05	0.00
	1.99	1.00	1.95	1.99	1.93	—	—	1.00	0.00	0.08	0.05	0.01

Fig.3 IRC scans of the transition states in S0 and T1 state(A) Reactant S0-MIN-2NN, transition state TS(S0,2NN?ISO), product S0?MIN?ISO; (B) transient intermediates, reactant T1-MIN-2NN, transition state TS(T1,2NN?M), TS(T1,M?ISO), product T1-MIN-ISO.

Fig.4 Potential energy scans connecting S0-MIN-ISO, S1-MIN-ISO and T1-MIN-ISO along the N—O reaction coordinate(A) S0-MIN-ISO; (B) S1-MIN-ISO; (C) T1-MIN-ISO.

Fig.5 Excited state decay kinetics and photo-dissociation channels for 2NN

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