Study on the Decay Dynamic of Excited State and Photodissociation Channel for 2-Nitronaphthalene†

doi:10.7503/cjcu20170768

Abstract

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

CLC Number:

O641

TrendMD:

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

Figures/Tables 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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