Rotational analysis of the perpendicular vibrational bands of 32SF6-Ar and 32SF6-34SF6 complexes at 10.6 μm

YUAN Hongrui; LIU Yun; LI Xiang; DUAN Chuanxi

doi:10.7498/aps.74.20250726

Abstract

Sulfur hexafluoride (SF₆) is widely used in the electrical and electronic industries. It is also an important green-house gas. The study of spectra and structures of weakly bound complexes containing SF₆ is helpful to gain a deep understanding of the intermolecular interactions between SF₆ and other atoms or molecules. The rotationally resolved spectrum of the perpendicular vibrational band of ³²SF₆-Ar in the ³²SF₆ v₃ band region has been reported previously but the rotational analysis was not completed. In this work, this vibrational band of ³²SF₆-Ar is re-investigated. The jet-cooled rovibrational spectra of SF₆/Ar/He gas mixtures are measured by a continuous-wave distributed feed-back quantum cascade laser (DFB-QCL) at 10.6 μm with a segmented- rapid-scan data acquisition scheme. The gas mixture (SF₆∶Ar∶He = 0.12∶1∶100) is expanded into a cylinder vacuum chamber through a 0.8 mm pin-hole nozzle. The probe laser is reflected about 90 times by a pair of astigmatic mirrors inside the chamber. The observed spectrum is analyzed by the standard symmetric-top Hamiltonian with the program PGOPHER. When the resonance interaction between the l = $ \pm 1 $ levels in the double-degenerate excited vibrational state of ³²SF₆-Ar is considered, which was ignored in previous studies, a successful rotational analysis of the perpendicular vibrational band is conducted. The band-origin of the perpendicular band is determined to be v₀ = 947.45300(58) cm^–1 and the resonance interaction parameter is q = –0.002325(70) cm^–1. A set of absorption lines close to the Q branch of the ³²SF₆ v₃ band is tentatively assigned to the perpendicular vibrational band of ³²SF₆-³⁴SF₆ complex. This band is heavily overlapped by the monomer lines so that very few lines can be assigned. The band-origin of this band is estimated to be 948.1181(12) cm^–1. These results will be useful for developing highly accurate intermolecular potential energy surfaces for SF₆-Ar complex and SF₆ dimer in the future.

Keywords:

Authors and contacts

1.
Research Institute of Physical and Chemical Engineering for Nuclear Industry, Tianjin 300180, China
2.
National Key Laboratory of Particle Transport and Separation Technology, Tianjin 300180, China
3.
College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China

Corresponding author: DUAN Chuanxi, duanchx@ccnu.edu.cn

Funds: Project supported by the Young Talents Research Project of China National Nuclear Corporation, the National Key Laboratory of Particle Transport and Separation Technology (Grant No. KGKF-2024-4) and the Fundamental Research Funds for the Central Universities of China (Grant No. CCNU25JC021).

FullText HTML

References

[1]	Makarov G N 2005 Phys. -Usp. 48 37 Google Scholar
[2]	Zellweger J M, Philippoz J M, Melinon P, Monot, van den Bergh H 1984 Phys. Rev. Lett. 52 522 Google Scholar
[3]	Eerkens J W 1998 Laser Part. Beams 16 295 Google Scholar
[4]	Makarov G N 2015 Phys. -Usp. 58 670 Google Scholar
[5]	李业军, 郭静, 马俊平, 唐显, 李鑫, 闫冰 2022 物理学报 71 243401 Google Scholar Li Y G, Guo J, Ma J P, Tang X, Li X, Yan B 2022 Acta Phys. Sin. 71 243401 Google Scholar
[6]	Geraedts J, Setiadi S, Stolte S, Reuss J 1981 Chem. Phys. Lett. 78 277 Google Scholar
[7]	Geraedts J, Stolte S, Reuss J 1982 Zeit. Phys. A 304 167 Google Scholar
[8]	Urban R D, Takami M 1995 J. Chem. Phys. 103 9132 Google Scholar
[9]	Asselin P, Potapov A, Turner A C, Boudon V, Bruel L, Gaveau M A, Mons M 2017 Phy. Chem. Chem. Phys. 19 17224 Google Scholar
[10]	Kolomiitsova T D, Mielke Z, Shchepkin D N, Tokhadze K G 2002 Chem. Phys. Lett. 357 181 Google Scholar
[11]	Tokhadze I K, Kolomiitsova T D, Shchepkin D N, Tokhadze K G, Mielke Z 2009 J. Phys. Chem. A 113 6334 Google Scholar
[12]	van Bladel J W I, van der Avoird A 1990 J. Chem. Phys. 92 2837 Google Scholar
[13]	Vazhappilly T, Marjolin A, Jordan K J 2016 J. Phys. Chem. B 120 1788 Google Scholar
[14]	Hartmann M, Miller R E, Toennies J P, Vilesov A F 1996 Science 272 1631 Google Scholar
[15]	Asselin P, Turner A C, Bruel L, Brenner V, Gaveau M A, Mons M 2018 Phy. Chem. Chem. Phys. 20 28105 Google Scholar
[16]	Luo W, Zhang Y L, Li W G, Duan C X 2017 J. Mol. Spectrosc. 334 22 Google Scholar
[17]	袁洪瑞, 刘涛, 朱天鑫, 刘云, 李响, 陈杨, 段传喜 2023 物理学报 72 063301 Google Scholar Yuan H R, Liu T, Zhu T X, Liu Y, Li X, Chen Y, Duan C X 2023 Acta Phys. Sin. 72 063301 Google Scholar
[18]	Liu Y, Li X, Qing T, Duan C X 2025 J. Phys. Chem. A 129 2259 Google Scholar
[19]	Gordon I E, Rothman L S, Hargreaves R J, et al. 2022 J. Quant. Spectrosc. Radiat. Transfer 277 107949 Google Scholar
[20]	Western C M 2017 J. Quant. Spectrosc. Radiat. Transfer. 186 221 Google Scholar
[21]	Suas-David N, Kulkarni V, Benidar A, Kassi S, Georges R 2016 Chem. Phys. Lett. 659 209 Google Scholar

Cited By

图 1 SF₆/Ar/He混合气体在³²SF₆单体v₃带附近的超声射流吸收光谱, 图中标(*), (⊥)和(//)的谱峰分别是³²SF₆单体v₃带、³²SF₆-Ar复合物的垂直谱带和平行谱带的带心对应的频率位置

Figure 1. The absorption spectrum of supersonic jet with SF₆/Ar/He gas mixtures at the v₃ band region of ³²SF₆, the approximate band-origin position is marked with (*) for the v₃ band of ³²SF₆ monomer, (⊥) for the perpendicular band, and (//) for the parallel band of ³²SF₆-Ar complex, respectively.

DownLoad: Full-Size Img PowerPoint

图 2 ³²SF₆单体和³²SF₆-Ar复合物的吸收光谱　(a) 实验测量光谱; (b) ³²SF₆-Ar复合物平行和垂直谱带的模拟光谱; (c) ³²SF₆单体的模拟光谱(考虑多普勒分裂); (d) ³²SF₆单体的模拟光谱(不考虑多普勒分裂)

Figure 2. The absorption spectrum of ³²SF₆ monomer and ³²SF₆-Ar complex: (a) Observed spectrum; (b) simulated spectrum of the parallel and perpendicular bands of ³²SF₆-Ar; (c) simulated spectrum of ³²SF₆ monomer with Doppler splitting; (d) simulated spectrum of ³²SF₆ monomer without Doppler splitting.

DownLoad: Full-Size Img PowerPoint

图 3 ³²SF₆单体v₃基频带头附近的吸收光谱　(a) 实验测量光谱, 为了放大显示复合物的谱线, 单体的吸收谱线上部已被截断; (b) ³²SF₆-³⁴SF₆的模拟光谱, 线宽0.005 cm^–1, 转动温度 3 K

Figure 3. An expanded view of the absorption spectrum close to the v₃ band-origin of ³²SF₆: (a) Observed spectrum, the absorption lines of the monomer are truncated in order to view the lines of the complex; (b) simulated spectrum of ³²SF₆-³⁴SF₆, assuming a linewidth of 0.005 cm^–1 and a rotational temperature of 3 K.

DownLoad: Full-Size Img PowerPoint

表 1 ³²SF₆-Ar复合物的分子参数 (单位: cm^–1)^a

Table 1. Molecular parameters of ³²SF₆-Ar complex (in cm^–1)^a.

	参数	Ref. [15]	This work
基态	A"	0.0874^b	0.0874^b
基态	B''	0.022765(45)	0.022739(39)
平行谱带	v₀	946.97950(48)	946.97987(46)
	A'	0.086804(85)	0.08726(11)
	B'	0.020733(36)	0.020739(31)
垂直谱带	v₀	947.392^c	947.45300(58)
	A'	—	0.08844(12)
	B'	—	0.023750(57)
	ξ	—	0.6974(19)
	q	—	–0.002325(70)
注: ^a 括号中的数字为标准偏差, 与参数值的最后两位对齐; ^b 固定于从头计算得到的值; ^c ^RQ(J, 0)支的峰值位置.

DownLoad: CSV

表 2 ³²SF₆-Ar复合物的谱线频率 (单位: cm^–1)

Table 2. Spectral line frequency of ³²SF₆-Ar complex (in cm^–1).

J'	K'	J''	K''	Obs. freq.	Cal. freq.	v_obs–v_cal
5	0	6	0	946.6470	946.6470	0
4	0	5	0	946.7109	946.7125	–0.0016
3	0	4	0	946.7724	946.7740	–0.0016
2	0	3	0	946.8324	946.8314	0.0010
2	1	3	1	946.8326	946.8333	–0.0007
2	2	3	2	946.8393	946.8389	0.0005
1	0	2	0	946.8879	946.8849	0.0030
1	1	2	1	946.8882	946.8868	0.0015
3	3	3	3	946.9726	946.9726	0
2	2	2	2	946.9785	946.9753	0.0032
1	0	0	0	947.0217	947.0213	0.0004
2	0	1	0	947.0586	947.0588	–0.0003
2	1	1	1	947.0598	947.0607	–0.0009
3	0	2	0	947.0914	947.0923	–0.0009
3	1	2	1	947.0932	947.0942	–0.0010
4	0	3	0	947.1204	947.1218	–0.0014
4	1	3	1	947.1220	947.1236	–0.0017
4	2	3	2	947.1283	947.1292	–0.0009
4	3	3	3	947.1364	947.1385	–0.0021
5	0	4	0	947.1476	947.1473	0.0003
5	1	4	1	947.1479	947.1491	–0.0012
5	2	4	2	947.1557	947.1547	0.0010
6	0	5	0	947.1709	947.1687	0.0021
6	2	5	2	947.1768	947.1762	0.0006
7	0	6	0	947.1846	947.1862	–0.0016
7	2	6	2	947.1949	947.1936	0.0012
8	0	7	0	947.2007	947.1997	0.0010
3	1	4	2	947.2095	947.2096	–0.0001
3	1	4	0	947.2375	947.2385	–0.0010
2	1	3	2	947.2528	947.2520	0.0008
2	1	3	0	947.2719	947.2710	0.0010
1	1	2	2	947.2935	947.2935	0
1	1	2	0	947.3059	947.3077	–0.0019
3	1	3	0	947.3920	947.3925	–0.0005
4	0	4	1	947.3920	947.3917	0.0003
3	3	3	2	947.4224	947.4216	0.0007
4	3	4	2	947.4366	947.4367	–0.0001
1	1	0	0	947.4441	947.4442	0
2	1	1	0	947.5001	947.4983	0.0018
2	2	1	1	947.5002	947.4997	0.0005
3	3	2	2	947.5575	947.5581	–0.0006
3	1	2	0	947.5578	947.5569	0.0009
4	4	3	3	947.6189	947.6186	0.0003
4	1	3	0	947.6197	947.6197	0
5	4	4	3	947.6821	947.6825	–0.0004
5	3	4	2	947.6843	947.6846	–0.0004

DownLoad: CSV

表 3 SF₆二聚体的分子参数 (单位: cm^–1)^a

Table 3. Molecular parameters of SF₆ dimer (in cm^–1)^a.

Parameter	(³²SF₆)₂^b	³²SF₆-³⁴SF₆
A''	0.04554(6)	0.04554^c
B''	0.0083811(26)	0.0083811^c
$ {\nu }_{0}^{\perp } $	956.09502(37)	948.1181(12)
A'	0.04551(fixed)	0.04551^c
B'	0.0083803(28)	0.0083803^c
ξ (unitless)	0.66796(70)	0.66796^c
注: ^a 括号中的数字为标准偏差, 与参数值的最后两位对齐; ^b 文献[9]; ^c 固定于(³²SF₆)₂对应参数的值.

DownLoad: CSV

表 4 ³²SF₆-³⁴SF₆复合物的谱线频率 (单位: cm^–1)

Table 4. Spectral line frequency of ³²SF₆-³⁴SF₆ complex (in cm^–1).

J'	K'	J''	K''	Obs. freq.	Cal. freq.	v_obs-v_cal
3	2	4	3	947.9943	947.9876	0.0068
2	2	3	3	948.0101	948.0043	0.0058
4	1	5	0	948.0178	948.0110	0.0068
12	3	12	4	948.0422	948.0412	0.0010
11	2	11	3	948.0574	948.0545	0.0029
11	1	11	2	948.0665	948.0678	–0.0013
11	0	11	1	948.0803	948.0812	–0.0010
11	2	11	1	948.1048	948.1082	–0.0034
11	3	11	2	948.1132	948.1218	–0.0086
12	4	12	3	948.1283	948.1354	–0.0071
5	1	4	0	948.1766	948.1786	–0.0020

DownLoad: CSV

[1]	Makarov G N 2005 Phys. -Usp. 48 37 Google Scholar
[2]	Zellweger J M, Philippoz J M, Melinon P, Monot, van den Bergh H 1984 Phys. Rev. Lett. 52 522 Google Scholar
[3]	Eerkens J W 1998 Laser Part. Beams 16 295 Google Scholar
[4]	Makarov G N 2015 Phys. -Usp. 58 670 Google Scholar
[5]	李业军, 郭静, 马俊平, 唐显, 李鑫, 闫冰 2022 物理学报 71 243401 Google Scholar Li Y G, Guo J, Ma J P, Tang X, Li X, Yan B 2022 Acta Phys. Sin. 71 243401 Google Scholar
[6]	Geraedts J, Setiadi S, Stolte S, Reuss J 1981 Chem. Phys. Lett. 78 277 Google Scholar
[7]	Geraedts J, Stolte S, Reuss J 1982 Zeit. Phys. A 304 167 Google Scholar
[8]	Urban R D, Takami M 1995 J. Chem. Phys. 103 9132 Google Scholar
[9]	Asselin P, Potapov A, Turner A C, Boudon V, Bruel L, Gaveau M A, Mons M 2017 Phy. Chem. Chem. Phys. 19 17224 Google Scholar
[10]	Kolomiitsova T D, Mielke Z, Shchepkin D N, Tokhadze K G 2002 Chem. Phys. Lett. 357 181 Google Scholar
[11]	Tokhadze I K, Kolomiitsova T D, Shchepkin D N, Tokhadze K G, Mielke Z 2009 J. Phys. Chem. A 113 6334 Google Scholar
[12]	van Bladel J W I, van der Avoird A 1990 J. Chem. Phys. 92 2837 Google Scholar
[13]	Vazhappilly T, Marjolin A, Jordan K J 2016 J. Phys. Chem. B 120 1788 Google Scholar
[14]	Hartmann M, Miller R E, Toennies J P, Vilesov A F 1996 Science 272 1631 Google Scholar
[15]	Asselin P, Turner A C, Bruel L, Brenner V, Gaveau M A, Mons M 2018 Phy. Chem. Chem. Phys. 20 28105 Google Scholar
[16]	Luo W, Zhang Y L, Li W G, Duan C X 2017 J. Mol. Spectrosc. 334 22 Google Scholar
[17]	袁洪瑞, 刘涛, 朱天鑫, 刘云, 李响, 陈杨, 段传喜 2023 物理学报 72 063301 Google Scholar Yuan H R, Liu T, Zhu T X, Liu Y, Li X, Chen Y, Duan C X 2023 Acta Phys. Sin. 72 063301 Google Scholar
[18]	Liu Y, Li X, Qing T, Duan C X 2025 J. Phys. Chem. A 129 2259 Google Scholar
[19]	Gordon I E, Rothman L S, Hargreaves R J, et al. 2022 J. Quant. Spectrosc. Radiat. Transfer 277 107949 Google Scholar
[20]	Western C M 2017 J. Quant. Spectrosc. Radiat. Transfer. 186 221 Google Scholar
[21]	Suas-David N, Kulkarni V, Benidar A, Kassi S, Georges R 2016 Chem. Phys. Lett. 659 209 Google Scholar

[1]	Fang De-Yin, Fan Xu-Yang, Wei An, Wang Lu-Xia. Coherent excitation energy transfer processes in two-dimensional para-sexiphenyl molecular clusters. Acta Physica Sinica, 2023, 72(19): 197301. doi: 10.7498/aps.72.20230476
[2]	Li Xiang, Liu Yun, Zhu Tian-Xin, Duan Chuan-Xi. New rovibrational subbands of Ar-D₂O complex in the D₂O bending mode region. Acta Physica Sinica, 2023, 72(1): 013401. doi: 10.7498/aps.72.20221728
[3]	Yuan Hong-Rui, Liu Tao, Zhu Tian-Xin, Liu Yun, Li Xiang, Chen Yang, Duan Chuan-Xi. High-resolution jet-cooled laser absorption spectra of SF₆ at 10.6 μm. Acta Physica Sinica, 2023, 72(6): 063301. doi: 10.7498/aps.72.20222285
[4]	Zhao Hai-Sheng, Xu Zhao-Hui, Gao Jing-Fan, Xu Zheng-Wen, Wu Jian, Feng Jie, Xu Bin, Xue Kun, Li Hui, Ma Zheng-Zheng. Early time effects produced by neutral gas ionospheric chemical release. Acta Physica Sinica, 2018, 67(1): 019401. doi: 10.7498/aps.67.20171620
[5]	Zhao Hai-Sheng, Xu Zheng-Wen, Wu Zhen-Sen, Feng Jie, Wu Jian, Xu Bin, Xu Tong, Hu Yan-Li. A three-dimensional refined modeling for the effects of SF6 release in ionosphere. Acta Physica Sinica, 2016, 65(20): 209401. doi: 10.7498/aps.65.209401
[6]	Zhang Xiu-Rong, Wu Li-Qing, Rao Qian. Theoretical study of electronic structure and optical properties of OsnN0,(n=1 6) clusters. Acta Physica Sinica, 2011, 60(8): 083601. doi: 10.7498/aps.60.083601
[7]	Wu Yang, Duan Hai-Ming. Study of structure evolution of (C60)N clusters usingLennard-Jones atom-atom potential. Acta Physica Sinica, 2011, 60(7): 076102. doi: 10.7498/aps.60.076102
[8]	Peng Zhi-Min, Ding Yan-Jun, Zhai Xiao-Dong. Measurements of rotational and vibrational temperatures based on flame emission spectroscopy. Acta Physica Sinica, 2011, 60(10): 104702. doi: 10.7498/aps.60.104702
[9]	Fan Qun-Chao, Feng Hao, Sun Wei-Guo. Studies on the full vibrational spectra and dissociation energies of some diatomic ions. Acta Physica Sinica, 2010, 59(1): 203-209. doi: 10.7498/aps.59.203
[10]	Miao Jing-Wei, Wang Pei-Lu, Zhu Zhou-Sen, Yuan Xue-Dong, Wang Hu, Yang Chao-Wen, Shi Mian-Gong, Miao Lei, Sun Wei-Li, Zhang Jing, Liao Xue-Hua. Photoluminescence spectrum of monocrystalline Si implanted by nitrogen cluster ions. Acta Physica Sinica, 2008, 57(4): 2174-2178. doi: 10.7498/aps.57.2174
[11]	Shi De-Heng, Sun Jin-Feng, Zhu Zun-Lüe, Ma Heng, Yang Xiang-Dong. Investigation on vibrational levels, inertial rotation and centrifugal distortion constants of 7Li2(X1Σ+g). Acta Physica Sinica, 2008, 57(1): 165-171. doi: 10.7498/aps.57.165
[12]	Shi De-Heng, Sun Jin-Feng, Liu Yu-Fang, Ma Heng, Zhu Zun-Lue, Yang Xiang-Dong. Investigation of analytic potential energy function, vibrational levels and inertial rotation constants for the 23Πu state of spin-aligned dimer 7Li2. Acta Physica Sinica, 2007, 56(8): 4454-4460. doi: 10.7498/aps.56.4454
[13]	Chen Xiao-Hong, Gao Tao, Zhu Zheng-He, Luo Shun-Zhong. Study on the structure and stability of the Al2O3Hx(x=1—3) molecules by density function theory. Acta Physica Sinica, 2007, 56(1): 178-185. doi: 10.7498/aps.56.178
[14]	Fang Fang, Jiang Gang, Wang Hong-Yan. Structures and properties of small bimetallic PdnPbm(n+m≤5) clusters. Acta Physica Sinica, 2006, 55(5): 2241-2248. doi: 10.7498/aps.55.2241
[15]	Ye Zi-Yan, Zhang Qing-Yu. ＭｏｌｅｃｕｌａｒｄｙｎａｍｉｃｓｓｉｍｕｌａｔｉｏｎｓｏｆｌｏｗｅｎｅｒｇｙＰｔｃｌｕｓｔｅｒｄｅｐｏｓｉｔｉｏｎ. Acta Physica Sinica, 2002, 51(12): 2798-2803. doi: 10.7498/aps.51.2798
[16]	WANG PEI-LU, LIU ZHONG-YANG, ZHENG SI-XIAO, LIAO XIAO-DONG, YANG CHAO-WEN, TANG A-YOU, SHI MIAN-GONG, YANG BEI-FANG, MIAO JING-WEI. STUDIES ON THE FEATURE OF Si(111) SURFACE IMPLANTED BY NITROGEN ATOM,MOLECULE AND CLUSTER IONS. Acta Physica Sinica, 2001, 50(5): 860-864. doi: 10.7498/aps.50.860
[17]	YAN HONG, CHANG ZHE, GUO HAN-YING. q-ROTATING OSCILLATOR MODEL (I)——q-Oscillator and Vibrational Spectra of Diatomic Molecules. Acta Physica Sinica, 1991, 40(9): 1377-1387. doi: 10.7498/aps.40.1377
[18]	. . Acta Physica Sinica, 1965, 21(8): 1570-1572. doi: 10.7498/aps.21.1570
[19]	A. T. Kiang. Vibrational-Rotational Spectrum and Potential Function of a Linenr Asymmetrical Triatomlc Molecule. Acta Physica Sinica, 1944, 5(1): 49-63. doi: 10.7498/aps.5.49
[20]	. . Acta Physica Sinica, 1933, 1(1): 1-37. doi: 10.7498/aps.1.1

Catalog

Vol. 74, Issue 17 - 2025-09-05

Metrics

Abstract views: 388
PDF Downloads: 11
Cited By: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

Search

Article

留言板

Rotational analysis of the perpendicular vibrational bands of ³²SF₆-Ar and ³²SF₆-³⁴SF₆complexes at 10.6 μm

Abstract

Authors and contacts

Corresponding author: DUAN Chuanxi, duanchx@ccnu.edu.cn

FullText HTML

References

Cited By

Catalog

Metrics

Authors

Referees

About Journal

About

Search

Article

留言板