(SO₂)₂在SO₂单体反对称伸缩振动区域的振转光谱

Rovibrational Spectrum of (SO₂)₂ Complex in the Asymmetric Stretching Region of SO₂

摘要

利用中红外连续可调谐外腔量子级联激光器结合脉冲超声喷射红外吸收光谱技术, 在SO₂分子ν₃反对称伸缩振动带附近得到(SO₂)₂的高分辨振转光谱. 实验共标识出490条红外跃迁, 其中, 电子供体(ED)谱带包含395条跃迁(J≤29, K_a≤11), 电子受体(EA)谱带包含95条跃迁(J≤21, K_a≤8). 结合已报道的微波光谱数据、SO₂单体v₁激发态光谱以及实验新测得的光谱数据, 基于非对称陀螺哈密顿量进行最小二乘法全局拟合, 得到了包括转动常数和离心畸变常数在内的精确的基态和激发态光谱参数. 结果表明, (SO₂)₂ ED和EA谱带的带头位置分别为1355.77424(14)和1356.34969(27) cm⁻¹, 相较于SO₂单体ν₃带带头分别产生6.29和5.71 cm⁻¹的红移.

Abstract

High-resolution rovibrational spectra of (SO₂)₂ in the ν ₃ asymmetric stretching region of SO₂ were measured using a mid-infrared continuously tunable external cavity quantum cascade laser combined with pulsed supersonic jet infrared absorption spectroscopy. A total of 490 infrared transitions were identified, including 395 transitions in the electron-doner (ED) band (J≤29, K _a≤11) and 95 transitions in the electron-acceptor (EA) band (J≤21, K _a≤8). By integrating previously reported microwave spectral data, spectral data of SO₂ monomer in the v ₁ excited state, and the newly measured spectral data in this work, global fitting was performed based on the asymmetric top Hamiltonian, yielding accurate ground and excited state spectroscopic parameters including rotational constants and centrifugal distortion constants. The band origins of the ED and EA bands of (SO₂)₂ are 1355.77424(14) and 1356.34969(27) cm⁻¹, respectively, exhibiting red shifts of 6.29 and 5.71 cm⁻¹ compared to the band origin of the v ₃ band of SO₂ monomer.

关键词

振转光谱 / 二氧化硫二聚体 / 超声分子束 / 振动频移

Key words

Rovibrational spectrum / Sulfur dioxide dimer / Supersonic jet / Vibrational frequency shift

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基金资助

国家自然科学基金(12464038)

国家自然科学基金(12564035)

江西省自然科学基金(20242BAB20031)

江西省自然科学基金(20252BAC240159)

河南省科技攻关项目(252102211100)

江西省教育厅科技项目(GJJ2401902)

南昌师范学院博士科研启动基金(NSBSJJ2023010)