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Abstract

In this work, the molecular structure and energy of some critical points in nonradiative relaxation process of the excited state of pentafluoropyridine are studied through quantum chemistry calculation. The structures and the vertical excitation energies and adiabatic excitation energies of the ground state and two lowest exited states are calculated. The geometry of the ground state is a planar structure with C _2vsymmetry, while the geometries of the two lowest excited states are half-boat structures with out-of-plane distortions. Furthermore, the topology structures and energy of the conical intersections of S ₂/S ₁, S ₁/S ₀and S ₂/S ₀are determined. The topology structures of the conical intersections S ₂/S ₁, S ₁/S ₀and S ₂/S ₀in the branching space are all peaked with asymmetric structures, and are determined to be structure of boat, half-boat, and chair, respectively. Their corresponding energy values are estimated at 6.39, 5.16 and 8.51 eV, respectively. The results show that the primary non-adiabatic relaxation pathway is the wavepacket of the S ₂state rapidly evolving into the S ₁state via the S ₂/S ₁, and then directly relaxing to the ground state via the S ₁/S ₀. In addition, the probability of directly relaxing to the ground state through S ₂/S ₀is smaller.

Keywords:

Authors and contacts

Li Duo-Duo^1,2,
Zhang Song^1,2

Corresponding author:Zhang Song,zhangsong@wipm.ac.cn

Funds:Project supported by the National Key Research and Development Program of China (Grant No. 2019YFA0307700), the National Natural Science Foundation of China (Grant Nos. 12274418, 22273116, 11974381, 12074389, 21873114), and the Knowledge Innovation Program of Wuhan-Basic Research, China (Grant No. 2022010801010134).

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Cited By

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结构参数	S₁			S₂
结构参数	B3LYP/ 6-311G*	M062X/ 6-311G*	SA-CASSCF/ 6-311G*	B3LYP/ 6-311G*	M062X/ 6-311G*	SA-CASSCF/ 6-311G*
C₁—F₁	1.32	1.31	1.31	1.34	1.31	1.29
C₂—F₂	1.34	1.33	1.33	1.34	1.33	1.33
C₃—F₃	1.41	1.37	1.37	1.39	1.37	1.29
C₄—F₄	1.34	1.33	1.33	1.34	1.33	1.32
C₅—F₅	1.32	1.31	1.31	1.34	1.31	1.30
C₁—N	1.32	1.32	1.32	1.33	1.32	1.44
C₅—N	1.32	1.32	1.32	1.33	1.32	1.36
C₁—C₂	1.43	1.43	1.43	1.38	1.43	1.35
C₂—C₃	1.40	1.40	1.40	1.44	1.40	1.43
C₃—C₄	1.40	1.40	1.40	1.44	1.40	1.47
C₄—C₅	1.43	1.43	1.43	1.38	1.43	1.34
C₁—C₅	2.20	2.18	2.21	2.29	2.18	2.36
C₂—C₄	2.28	2.28	2.36	2.45	2.28	2.52
N—C₁—C₂—C₅	3.83	5.31	1.13	3.07	5.42	20.69
C₃—C₂—C₁—C₄	13.26	13.33	0.30	16.25	13.16	20.64
F₃—C₃—C₄—C₁	54.38	52.09	45.11	75.49	51.89	55.04
F₄—C₄—C₅—C₁	13.68	14.05	3.13	12.19	14.58	32.02
F₅—C₅—C₄—C₂	6.96	9.10	2.96	7.32	9.66	18.20

DownLoad: CSV

Methods	S₁				S₂
Methods	VEEs	Dev/%	AEEs	Dev/%	VEEs	AEEs
Exp.^a)	4.88	—	4.60	—	—	—
RI-SCS-CC2^a)	5.10	4.5	4.60	0	6.35	—
XMCQDPT2^a)	4.89	0.2	4.41	4.1	6.23	5.26
B3LYP	5.33	9.2	4.41	4.1	6.28	5.26
SA-CASSCF(8, 8)	5.47	12.1	4.84	5.2	6.92	6.69
M062X	5.63	9.8	4.80	4.3	6.50	6.15^b)
CASPT2	5.02	2.9	4.41	4.1	6.33	—
注:^a)来自参考文献[22];^b)基于M062X/6-31G*的结果

DownLoad: CSV

参数	S₂/S₁	S₁/S₀	S₂/S₀
C₁—F₁	1.30	1.30	1.31
C₂—F₂	1.32	1.31	1.30
C₃—F₃	1.30	1.32	1.32
C₄—F₄	1.32	1.31	1.30
C₅—F₅	1.30	1.30	1.31
C₁—N	1.45	1.31	1.48
C₅—N	1.29	1.33	1.42
C₁—C₂	1.47	1.46	1.49
C₂—C₃	1.39	1.46	1.48
C₃—C₄	1.49	1.47	1.47
C₄—C₅	1.45	1.45	1.49
N—C₁—C₂—C₅	29.72	2.15	22.59
C₃—C₂—C₁—C₄	10.90	46.24	12.28
F₃—C₃—C₄—C₁	11.57	36.30	64.87
F₄—C₄—C₅—C₁	9.84	30.71	0.81

DownLoad: CSV

参数	S₁/S₀	S₂/S₁	S₂/S₀
σ_x/(eV·Å^–1)	–0.0047	0.1413	0.4016
σ_y/(eV·Å^–1)	–0.0207	0.0757	–0.0001
${\varDelta }_{\mathrm{gh}} $	–0.9904	–0.9796	–0.8647
d_gh	1.5000	1.0212	0.6159

DownLoad: CSV

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Vol. 73, Issue 4 - 2024-02-20

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