Two-color resonance enhanced two-photon ionization and mass analyzed threshold ionization spectroscopy of <i>p</i>-chlorobenzonitrile

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Abstract

The vibrational features of p-chlorobenzonitrile in its first electronically excited state S ₁and cationic ground state D ₀have been investigated by two-color resonance enhanced two-photon ionization and mass analyzed threshold ionization spectroscopy. The excitation energy of S ₁← S ₀and the ionization energy of ³⁵Cl and ³⁷Cl isotopomers of p-chlorobenzonitrile are determined to be 35818 ± 2, and 76846 ± 5 cm ^–1, respectively. These two isotopomers have similar vibrational features. Most of the active vibrations in the S ₁and D ₀states are related to the motions of the in-plane ring deformation. The stable structures and vibrational frequencies of p-chlorobenzonitrile are also calculated by the B3LYP/aug-cc-pVDZ method for the S ₀and D ₀states, and TD-B3LYP/aug-cc-pVDZ method for the S ₁state. The changes in the molecular geometry are discussed in the S ₁← S ₀photoexcitation process and the D ₀← S ₁photoionization process. The comparisons between the transition energy of p-chlorophenol, p-chloroaniline, p-chloroanisole, and p-chlorobenzonitrile with those of phenol, anisole, aniline, and benzonitrile provide an insight into the substitution effect of Cl atom.

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Authors and contacts

Corresponding author:Zhao Yan,zhaoy@jzxy.edu.cn; Li Chang-Yong,lichyong@sxu.edu.cn

Funds:Project supported by the National Key R&D Program of China (Grant No. 2017YFA0304203), the Key Program of the National Natural Science Foundation of China (Grant No. 61835007), the National Natural Science Foundation of China (Grants Nos. 11904215, 61575115), the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China (Grant No. IRT_17R70), the 111 Project (Grant No. D18001), the Shanxi Provincial Higher Education Science and Technology Innovation Program, China (Grants Nos. 2020L0582, 2020L0599), the Shanxi Provincial Research Foundation for Basic Research, China (Grant No. 20210302124542), the Scientific Research Starting Foundation for Doctor, China (Grant No. 2019012), and the Fund for Shanxi ‘‘1331 Project” Key Subjects Construction, China.

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³⁵Cl		³⁷Cl		光谱归属^b
实验值^a	理论值^a	实验值^a	理论值^a	光谱归属^b
0		0		$ 0_0^0 $
139	141	139	141	$ 15_0^1 $, β(C—CN)
292	291	292	291	$ 9{\text{b}}_0^1 $, β(C—Cl)
310	300	309	300	$ 7{\text{a}}_0^1 $, β(CCC), ν (C—Cl)
457	454	457	454	$ 16{\text{b}}_0^1 $, γ(CCC)
504	495	504	495	$ 6{\text{b}}_0^1 $, β(CCC)
552	567	552	567	$ 12_0^1 $, β(CCC)
592	597	590	597	β(C—CN)
739	747	739	746	$ 6{\text{a}}_0^1 $, β(CCC)
816		818		$ 6{\text{b}}_0^17{\text{a}}_0^1 $
859		859		$ 12_0^17{\text{a}}_0^1 $
867		867		$ 6{\text{a}}_0^115_0^1 $
962	970	962	970	$ 18{\text{a}}_0^1 $, β(CH)
1002		1002		$ 6{\text{b}}_0^2 $
1054		1054		$ 6{\text{a}}_0^17{\text{a}}_0^1 $
1067	1055	1066	1055	$ 1_0^1 $, breathing
1149	1147	1149	1147	$ 9{\text{a}}_0^1 $, β(CH)
1176	1187	1176	1187	$ 13_0^1 $, ν(C—CN)
^a实验值是相对于对氯苯腈分子激发能(35818 cm^–1)的偏移, 理论值是TD-B3LYP/aug-cc-pVDZ方法计算的振动频率(校正因子0.984)
^bν, 伸缩振动; β, 苯环平面内的弯曲振动; γ, 垂直于苯环平面的弯曲振动

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³⁵Cl			³⁷Cl			光谱归属^b
S₁中间态		理论值^a	S₁中间态		理论值^a
S₁0⁰	S₁6b¹	理论值^a	S₁0⁰	S₁6b¹	理论值^a
0
346		347	343		344	7a¹, β(CCC) , ν (C—Cl)
	517	528		514	529	6b¹, β(CCC)
	587			584		6b¹11¹
601		598				12¹, β(CCC)
691		693	681		687	7a²
719		731	715		734	4¹, γ(C—CN)
778		772	778		775	6a¹, β(CCC)
	860			857		6b¹7a¹
947			947			7a¹12¹
	1032					6b²
1035		1040	1031		1031	7a³
1063						7a¹4¹
1110		1093	1116		1096	1¹, breathing
1127	1118			1118		6b¹12¹
	1205			1191		6b¹7a²
1223		1223	1227		1228	13¹, ν(C—CN)
	1236					6b¹4¹
	1292			1292		6b¹6a¹
1388		1390				8b¹, ν(CC)
	1549			1545		6b¹7a³
1572	1577	1569	1570			7a¹13¹
1608		1614	1612		1621	8a¹, ν(CC)
	1641			1631		6b¹1¹
^a实验值是相对于对氯苯腈分子电离能(76846 cm^–1)的偏移, 理论值是B3LYP/aug-cc-pVDZ方法计算的振动频率(校正因子0.981)
^bν, 伸缩振动; β, 苯环平面内的弯曲振动; γ, 垂直于苯环平面的弯曲振动

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结构参数	Exp.^a	S₀^b	S₁^c	D₀^b	Δ(S₁-S₀)	Δ(D₀-S₁)
键长/Å
C₁-C₂	1.397	1.406	1.432	1.433	0.026	0.008
C₂-C₃	1.384	1.393	1.429	1.373	0.036	–0.056
C₃-C₄	1.387	1.397	1.418	1.429	0.021	0.011
C₄-C₅	1.380	1.397	1.418	1.429	0.021	0.011
C₅-C₆	1.382	1.393	1.429	1.373	0.036	–0.056
C₆-C₁	1.386	1.406	1.432	1.433	0.026	0.001
C₄-Cl₇	1.745	1.755	1.733	1.695	–0.022	–0.038
C₁-C₈	1.454	1.436	1.414	1.413	–0.023	–0.001
C₈-N₉	1.110	1.163	1.171	1.170	0.008	–0.001
键角/°
C₁C₂C₃	119.1	120.2	119.5	119.6	–0.7	0.1
C₂C₃C₄	119.4	119.2	118.7	118.9	–0.5	0.2
C₃C₄C₅	121.7	121.4	122.7	121.9	1.3	–0.8
C₄C₅C₆	118.8	119.2	118.7	118.9	–0.5	0.2
C₅C₆C₁	120.2	120.2	119.5	119.6	–0.7	0.1
C₆C₁C₂	120.6	119.8	120.8	121.0	1.0	0.2
^a对氯苯腈分子的晶体结构参数^[31]
^bB3LYP/aug-cc-pVDZ方法理论计算的结构参数
^cTD-B3LYP/aug-cc-pVDZ方法理论计算的结构参数

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Molecule	E₁(S₁← S₀)	ΔE₁	E₂(D₀← S₁)	ΔE₂	IE	ΔIE
苯酚^[33]	36, 349	0	32, 276	0	68, 625	0
对氯苯酚^[30]	34, 813	–1537	33, 291	1015	68, 104	–521
苯甲醚^[34]	36, 383	0	30, 016	0	66, 399	0
对氯苯甲醚^[29]	34, 859	–1524	31, 253	1237	66, 112	–287
苯胺^[35]	34, 029	0	28, 242	0	62, 271	0
对氯苯胺^[23]	32, 573	–1456	29, 837	1593	62, 410	139
苯腈^[36]	36, 518	0	41, 972	0	78, 490	0
对氯苯腈	35, 818	–700	41, 028	–944	76, 846	–1644
对甲基苯腈^[37]	36, 222	–296	38, 933	–3039	75, 155	–2845
对氨基苯腈^[38]	33, 481	–3037	33, 012	–8960	66, 493	–11997
^aΔE₁, ΔE₂,和ΔIE是衍生物分子E₁,E₂跃迁能和IE电离能相对苯酚、苯甲醚、苯胺、苯腈E₁,E₂,IE能量的差值

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Vol. 71, Issue 10 - 2022-05-20

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