SF<sub>6</sub>分子的10.6 μm高分辨射流冷却激光吸收光谱

袁洪瑞; 刘涛; 朱天鑫; 刘云; 李响; 陈杨; 段传喜

doi:10.7498/aps.72.20222285

摘要

六氟化硫(SF₆)是一种长寿命的温室气体, 其红外吸收光谱对模拟大气辐射平衡非常重要. SF₆也是研究激光分离同位素原理和技术的典型体系之一. 由于SF₆分子较重, 其室温下的红外光谱非常密集, 给利用吸收光谱技术监测不同SF₆同位素分子的相对浓度带来很大困难. 本文利用超声射流冷却和像散型多程吸收池技术, 测量了³²SF₆和³³SF₆同位素分子在10.6 μm波段的高分辨红外激光吸收光谱. 处于振动基态的³²SF₆和³³SF₆分子在狭缝型超声射流中的转动温度约为10 K, 谱线线宽约为0.0008 cm^–1. 在此条件下观测到了SF₆一个新的热带, 其Q支的位置在941.0 cm^–1附近. 将其初步归属为³²SF₆的(v₁+v₂+v₃)–(v₁+v₂) 带, 对该热带进行简化的转动分析, 并讨论利用该热带和³³SF₆的v₃基频带进行³³SF₆/³²SF₆的相对浓度监测的可行性.

关键词:

Abstract

Sulfur hexafluoride (SF₆) is a greenhouse gas of very long lifetime. Its infrared absorption spectrum is very important in modeling the atmospheric radiation balances. The SF₆ is also a prototypical system for studying the principles and techniques of laser isotope separation using powerful infrared lasers. As a very heavy molecule, the infrared spectrum of SF₆ at room temperature is very dense, which poses a great challenge to monitoring the relative abundances of different SF₆ isotopomers by direct absorption spectroscopy. Supersonic jet expansions have been widely used to simplify the gas phase molecular spectra. In this work, astigmatic multi-pass absorption cell and distributed feed-back quantum cascade lasers (QCLs) are used to measure jet-cooled rovibrational absorption spectra of ³²SF₆ and ³³SF₆ at 10.6 μm. The spectrometer works in a segmented rapid-scan mode. The gas mixtures (SF₆∶Ar∶He = 0.12∶1∶100) are expanded through an 80 mm $ \times $ 300 μm pulsed slit nozzle. Two QCLs running at room temperature are used and each one covers a spectral range of about 3.0 cm^–1. The v₃ fundamental bands of both ³²SF₆ and ³³SF₆ are observed. The rotational temperature of ³²SF₆ and ³³SF₆ in the ground state in the supersonic jet are both estimated at 10 K and the linewidth is about 0.0008 cm^–1 by comparing the simulated spectrum with the observed spectrum with the PGOPHER program. A new weak vibrational band centered around 941.0 cm^–1 is observed and tentatively assigned to the (v₁+v₂+v₃)–(v₁+v₂) hot band of ³²SF₆. The effective Hamiltonian used to analyze the rovibrational spectrum of SF₆ is briefly introduced. A simplified rotational analysis for this hot band is performed with the XTDS program developed by the Dijon group. The band-origin of this hot band is determined to be 941.1785(21) cm^–1. The rotational temperature of this hot band is estimated at 50 K. A new scheme by measuring the jet-cooled absorption spectrum of this hot band of ³²SF₆ and the v₃ fundamental band of ³³SF₆ is proposed for measuring the relative abundance of ³³SF₆/³²SF₆.

Keywords:

作者及机构信息

1.
核工业理化工程研究院, 天津　300180

2.
粒子输运与富集技术国防科技重点实验室, 天津　300180

3.
华中师范大学物理科学与技术学院, 武汉　430079

通信作者: 段传喜, duanchx@mail.ccnu.edu.cn

基金项目: 粒子输运与富集技术国防科技重点实验室基金资助的课题

Authors and contacts

1.
Research Institute of Physical and Chemical Engineering for Nuclear Industry, Tianjin 300180, China

2.
Science and Technology on Particle Transport and Separation Laboratory, Tianjin 300180, China

3.
College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China

Corresponding author: Duan Chuan-Xi, duanchx@mail.ccnu.edu.cn

Funds: Project supported by the Fund of Science and Technology on Particle Transport and Separation Laboratory, China.

文章全文

参考文献

[1]	Geller L, Elkins J, Lobert J, Clarke A, Hurst D, Butler J, Myers R 1997 Geophys. Res. Lett. 24 675 Google Scholar
[2]	Makarov G N 2005 Phys. Usp. 48 37 Google Scholar
[3]	Zellweger J M, Philippoz J M, Melinon P, Monot, van den Bergh H 1984 Phys. Rev. Lett. 52 522 Google Scholar
[4]	Eerkens J W 1998 Laser Part. Beams 16 295 Google Scholar
[5]	Makarov G N 2015 Phys. Usp. 58 670 Google Scholar
[6]	Sai Prasad M B, Padma Nilaya J, Ghosh A, Biswas D J 2020 Chem. Phys. 538 110831 Google Scholar
[7]	Faye M, Boudon V, Loët M, Roy P, Manceron L 2017 J. Quant. Spectrosc. Radiat. Transfer 190 38 Google Scholar
[8]	Faye M, Manceron L, Roy P, Boudon V, Loët M 2018 J. Mol. Spectrosc. 348 37 Google Scholar
[9]	Ke H, Boudon V, Richard C, Madhur, Faye M, Manceron L 2020 J. Mol. Spectrosc. 368 111251 Google Scholar
[10]	Boudon V, Hepp M, Herman M, Pak I, Pierre G 1998 J. Mol. Spectrosc. 192 359 Google Scholar
[11]	Boudon V, Doménech J L, Bermejo D, Willner H 2004 J. Mol. Spectrosc. 228 392 Google Scholar
[12]	Boudon V, Doménech J L, Ramos A, Bermejo D, Willner H 2006 Mol. Phys. 104 2653 Google Scholar
[13]	Faye M, Manceron L, Roy P, Boudon V, Loëte M 2018 J. Mol. Spectrosc. 346 23 Google Scholar
[14]	Luo W, Zhang Y L, Li W G, Duan C X 2017 J. Mol. Spectrosc. 334 22 Google Scholar
[15]	Liu Z, Luo W, Duan C X 2019 J. Chem. Phys. 150 064302 Google Scholar
[16]	Li X, Liu Z, Duan C X 2021 J. Mol. Spectrosc. 377 111424 Google Scholar
[17]	Gordon I E, Rothman L S, Hargreaves R J, et al. 2022 J. Quant. Spectrosc. Radiat. Transfer 277 107949 Google Scholar
[18]	Western C M 2017 J. Quant. Spectrosc. Radiat. Transfer. 186 221 Google Scholar
[19]	Asselin P, Turner A C, Bruel L, Brenner V, Gaveau M A, Mons M 2018 Phys. Chem. Chem. Phys. 20 28105 Google Scholar
[20]	Rey M M, Chizhmakova I S, Nikitin A V, Tyuterev V G 2021 Phys. Chem. Chem. Phys. 23 12115 Google Scholar
[21]	Champion J P, Loëte M, Pierre G 1992 Spectroscopy of the Earth's Atmosphere and Interstellar Medium (San Diego: Academic Press) pp339–422
[22]	Boudon V, Champion J P, Gabard T, et al. 2004 J. Mol. Spectrosc. 228 620 Google Scholar
[23]	Wenger C, Boudon V, Rotger M, Sanzharov J P, Champion J P 2008 J. Mol. Spectrosc. 251 102 Google Scholar

施引文献

图 1 实验装置示意图

Fig. 1. Schematic diagram of the experimental setup.

下载: 全尺寸图片幻灯片

图 2 ³²SF₆单体v₃带附近的吸收光谱　(a) ³²SF₆单体v₃振动带的模拟光谱, 线宽0.0008 cm^–1 (～24 MHz), 转动温度10 K; (b)实验测量光谱

Fig. 2. Absorption spectrum at the v₃ band region of ³²SF₆: (a) The simulated spectrum of the v₃ band of ³²SF₆ with a linewidth of 0.0008 cm^–1 (～24 MHz) and a rotational temperature of 10 K; (b) the experimental spectrum.

下载: 全尺寸图片幻灯片

图 3 ³³SF₆单体v₃带附近的吸收光谱　(a) ³³SF₆单体v₃振动带的模拟光谱, 线宽0.0008 cm^–1 (～24 MHz), 转动温度10 K; (b)实验测量光谱

Fig. 3. Absorption spectrum at the v₃ band region of ³³SF₆: (a) The simulated spectrum of the v₃ band of ³³SF₆ with a linewidth of 0.0008 cm^–1 (～24 MHz) and a rotational temperature of 10 K; (b) the experimental spectrum.

下载: 全尺寸图片幻灯片

图 4 ³²SF₆单体热带的吸收光谱　(a) ³²SF₆单体热带的模拟光谱, 线宽0.0008 cm^–1 (～24 MHz), 转动温度50 K; (b)实验测量光谱

Fig. 4. Absorption spectrum of the tentatively assigned hot band of ³²SF₆. (a) The simulated spectrum of the hot band of ³²SF₆ with a linewidth of 0.0008 cm^–1 (～24 MHz) and a rotational temperature of 50 K; (b) the experimental spectrum.

下载: 全尺寸图片幻灯片

表 1 ³²SF₆的热带的分子参数

Table 1. Molecular parameters for the hot band of ³²SF₆

	Order	${ {\varOmega } }(K, n{ {\varGamma } })$	$ \left\{s\right\} $	$ \left\{s'\right\} $	Values^b/cm^–1
GS^a	0	2(0, 0 A_1g)	000000 A_1g	000000 A_1g	9.10756$ \times {10}^{-3} $
	2	4(0, 0 A_1g)	000000 A_1g	000000 A_1g	–7.2689$ \times {10}^{-9} $
	2	4(4, 0 A_1g)	000000 A_1g	000000 A_1g	1.2227$ \times {10}^{-10} $
Excited	0	0(0, 0 A_1g)	001000 F_1u	001000 F_1u	941.1785(21)
	1	1(1, 0 F_1g)	001000 F_1u	001000 F_1u	0.26651(10)
	2	2(0, 0 A_1g)	001000 F_1u	001000 F_1u	–1.149(32)$ \times {10}^{-4} $
	2	2(0, 0 E_1g)	001000 F_1u	001000 F_1u	–1.1162(33)$ \times {10}^{-4} $
注: ^a 基态分子参数固定于文献[9]的值; ^b 括号中的数字为标准偏差, 与参数值的最后两位对齐.

下载: 导出CSV

表 2 ³³SF₆的v₃基频带和³²SF₆的热带的部分谱线频率

Table 2. A part of observed transition frequencies of the v₃ fundamental band of ³³SF₆ and the hot band of ³²SF₆

频率/cm^–1
³³SF₆		³²SF₆
R(2)	939.181	P(3)	940.883
R(3)	939.238	P(4)	940.826
R(4)	939.294	P(5)	940.768
R(5)	939.350	P(6)	940.709

下载: 导出CSV

[1]	Geller L, Elkins J, Lobert J, Clarke A, Hurst D, Butler J, Myers R 1997 Geophys. Res. Lett. 24 675 Google Scholar
[2]	Makarov G N 2005 Phys. Usp. 48 37 Google Scholar
[3]	Zellweger J M, Philippoz J M, Melinon P, Monot, van den Bergh H 1984 Phys. Rev. Lett. 52 522 Google Scholar
[4]	Eerkens J W 1998 Laser Part. Beams 16 295 Google Scholar
[5]	Makarov G N 2015 Phys. Usp. 58 670 Google Scholar
[6]	Sai Prasad M B, Padma Nilaya J, Ghosh A, Biswas D J 2020 Chem. Phys. 538 110831 Google Scholar
[7]	Faye M, Boudon V, Loët M, Roy P, Manceron L 2017 J. Quant. Spectrosc. Radiat. Transfer 190 38 Google Scholar
[8]	Faye M, Manceron L, Roy P, Boudon V, Loët M 2018 J. Mol. Spectrosc. 348 37 Google Scholar
[9]	Ke H, Boudon V, Richard C, Madhur, Faye M, Manceron L 2020 J. Mol. Spectrosc. 368 111251 Google Scholar
[10]	Boudon V, Hepp M, Herman M, Pak I, Pierre G 1998 J. Mol. Spectrosc. 192 359 Google Scholar
[11]	Boudon V, Doménech J L, Bermejo D, Willner H 2004 J. Mol. Spectrosc. 228 392 Google Scholar
[12]	Boudon V, Doménech J L, Ramos A, Bermejo D, Willner H 2006 Mol. Phys. 104 2653 Google Scholar
[13]	Faye M, Manceron L, Roy P, Boudon V, Loëte M 2018 J. Mol. Spectrosc. 346 23 Google Scholar
[14]	Luo W, Zhang Y L, Li W G, Duan C X 2017 J. Mol. Spectrosc. 334 22 Google Scholar
[15]	Liu Z, Luo W, Duan C X 2019 J. Chem. Phys. 150 064302 Google Scholar
[16]	Li X, Liu Z, Duan C X 2021 J. Mol. Spectrosc. 377 111424 Google Scholar
[17]	Gordon I E, Rothman L S, Hargreaves R J, et al. 2022 J. Quant. Spectrosc. Radiat. Transfer 277 107949 Google Scholar
[18]	Western C M 2017 J. Quant. Spectrosc. Radiat. Transfer. 186 221 Google Scholar
[19]	Asselin P, Turner A C, Bruel L, Brenner V, Gaveau M A, Mons M 2018 Phys. Chem. Chem. Phys. 20 28105 Google Scholar
[20]	Rey M M, Chizhmakova I S, Nikitin A V, Tyuterev V G 2021 Phys. Chem. Chem. Phys. 23 12115 Google Scholar
[21]	Champion J P, Loëte M, Pierre G 1992 Spectroscopy of the Earth's Atmosphere and Interstellar Medium (San Diego: Academic Press) pp339–422
[22]	Boudon V, Champion J P, Gabard T, et al. 2004 J. Mol. Spectrosc. 228 620 Google Scholar
[23]	Wenger C, Boudon V, Rotger M, Sanzharov J P, Champion J P 2008 J. Mol. Spectrosc. 251 102 Google Scholar

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SF₆分子的10.6 μm高分辨射流冷却激光吸收光谱

High-resolution jet-cooled laser absorption spectra of SF₆ at 10.6 μm

摘要

Abstract

作者及机构信息

1.
核工业理化工程研究院, 天津　300180

2.
粒子输运与富集技术国防科技重点实验室, 天津　300180

3.
华中师范大学物理科学与技术学院, 武汉　430079

通信作者: 段传喜, duanchx@mail.ccnu.edu.cn

Authors and contacts

Corresponding author: Duan Chuan-Xi, duanchx@mail.ccnu.edu.cn

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SF6分子的10.6 μm高分辨射流冷却激光吸收光谱

High-resolution jet-cooled laser absorption spectra of SF6 at 10.6 μm

摘要

Abstract

作者及机构信息

1. 核工业理化工程研究院, 天津 300180 2. 粒子输运与富集技术国防科技重点实验室, 天津 300180 3. 华中师范大学物理科学与技术学院, 武汉 430079

通信作者: 段传喜, duanchx@mail.ccnu.edu.cn

Authors and contacts

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

Corresponding author: Duan Chuan-Xi, duanchx@mail.ccnu.edu.cn

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SF₆分子的10.6 μm高分辨射流冷却激光吸收光谱

High-resolution jet-cooled laser absorption spectra of SF₆ at 10.6 μm

1.
核工业理化工程研究院, 天津　300180

2.
粒子输运与富集技术国防科技重点实验室, 天津　300180

3.
华中师范大学物理科学与技术学院, 武汉　430079