H2、HD和D2中F1Σg+外井态的光谱研究

IF 1.4 4区 物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Journal of Molecular Spectroscopy Pub Date : 2023-03-01 DOI:10.1016/j.jms.2023.111778
K.-F. Lai, M. Beyer, W. Ubachs
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The wave function density at large internuclear separation is excited via two-photon transitions in the F<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> - X<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> system to probe ro-vibrational levels in the first F<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> outer well state of <em>gerade</em> symmetry. Combining with accurate knowledge of the X<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> (<span><math><mrow><mi>v</mi><mo>,</mo><mi>J</mi></mrow></math></span>) levels from advanced ab initio calculations, energies of rovibrational levels in the F<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> state are determined. For the H<sub>2</sub> isotopologue a three-laser scheme is employed yielding level energies at accuracies of <span><math><mrow><mn>4</mn><mo>×</mo><mn>1</mn><msup><mrow><mn>0</mn></mrow><mrow><mo>−</mo><mn>3</mn></mrow></msup></mrow></math></span> cm<sup>−1</sup> for F(<span><math><mrow><mi>v</mi><mo>=</mo><mn>0</mn><mo>,</mo><mi>J</mi></mrow></math></span>) up to <span><math><mrow><mi>J</mi><mo>=</mo><mn>21</mn></mrow></math></span> and for some low <span><math><mi>J</mi></math></span> values of F(<span><math><mrow><mi>v</mi><mo>=</mo><mn>1</mn></mrow></math></span>). A two-laser scheme was applied to determine level energies in H<sub>2</sub> for F(<span><math><mrow><mi>v</mi><mo>=</mo><mn>0</mn><mo>−</mo><mn>4</mn></mrow></math></span>) levels as well as for various F levels in HD and D<sub>2</sub>, also up to large rotational quantum numbers. The latter measurements in the two-laser scheme are performed at lower resolution and the accuracy is strongly limited to 0.5 cm<sup>−1</sup> by ac-Stark effects. For H<sub>2</sub> a new quasibound resonance X<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> (<span><math><mrow><mi>v</mi><mo>=</mo><mn>6</mn></mrow></math></span>, <span><math><mrow><mi>J</mi><mo>=</mo><mn>23</mn></mrow></math></span>) is detected through the Q(23) and O(23) transitions in the F0-X6 band. Also a quasi-bound resonance in D<sub>2</sub> is assigned, for the first time in this species: X<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> (<span><math><mrow><mi>v</mi><mo>=</mo><mn>17</mn></mrow></math></span> , <span><math><mrow><mi>J</mi><mo>=</mo><mn>15</mn></mrow></math></span>). The experimental results on F(<span><math><mrow><mi>v</mi><mo>,</mo><mi>J</mi></mrow></math></span>) level energies are compared with previously reported theoretical results from multi-channel quantum-defect calculations as well as with results from newly performed non-adiabatic quantum calculations.</p></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":1.4000,"publicationDate":"2023-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Spectroscopic study of the F1Σg+ outer well state in H2, HD and D2\",\"authors\":\"K.-F. Lai,&nbsp;M. Beyer,&nbsp;W. 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The wave function density at large internuclear separation is excited via two-photon transitions in the F<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> - X<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> system to probe ro-vibrational levels in the first F<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> outer well state of <em>gerade</em> symmetry. Combining with accurate knowledge of the X<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> (<span><math><mrow><mi>v</mi><mo>,</mo><mi>J</mi></mrow></math></span>) levels from advanced ab initio calculations, energies of rovibrational levels in the F<span><math><mrow><msup><mrow></mrow><mrow><mn>1</mn></mrow></msup><msubsup><mrow><mi>Σ</mi></mrow><mrow><mi>g</mi></mrow><mrow><mo>+</mo></mrow></msubsup></mrow></math></span> state are determined. 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引用次数: 0

摘要

硫化氢分子的双光子紫外光解用于在X1∑g+电子基态产生高激发振动能级的氢分子,高达离解能并进入准束缚区。光解前体H2S、HDS和D2S用于产生振动热的H2、HD和D2。在F1∑g+-X1∑g+系统中,通过双光子跃迁激发了核间大分离时的波函数密度,以探测gerade对称的第一个F1∑g+外阱态中的ro振动能级。结合高级从头计算中X1∑g+(v,J)能级的精确知识,确定了F1∑g+态的回旋能级的能量。对于H2等拓扑结构,采用三激光方案,对于F(v=0,J)至J=21和F(v=1)的一些低J值,产生精度为4×10−3 cm−1的能级能量。应用双激光方案来确定H2中F(v=0−4)能级以及HD和D2中各种F能级的能级能量,也可以达到大的旋转量子数。双激光方案中的后一种测量是在较低的分辨率下进行的,并且由于ac Stark效应,精度被严格限制在0.5 cm−1。对于H2,通过F0-X6带中的Q(23)和O(23)跃迁检测到一个新的准束缚共振X1∑g+(v=6,J=23)。此外,在D2中首次给出了准束缚共振:X1∑g+(v=17,J=15)。将F(v,J)能级能量的实验结果与先前报道的多通道量子缺陷计算的理论结果以及新进行的非绝热量子计算的结果进行了比较。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Spectroscopic study of the F1Σg+ outer well state in H2, HD and D2

Two-photon UV-photolysis of hydrogen sulfide molecules is applied to produce hydrogen molecules in highly excited vibrational levels in the X1Σg+ electronic ground state, up to the dissociation energy and into the quasibound region. Photolysis precursors H2S, HDS and D2S are used to produce vibrationally hot H2, HD and D2. The wave function density at large internuclear separation is excited via two-photon transitions in the F1Σg+ - X1Σg+ system to probe ro-vibrational levels in the first F1Σg+ outer well state of gerade symmetry. Combining with accurate knowledge of the X1Σg+ (v,J) levels from advanced ab initio calculations, energies of rovibrational levels in the F1Σg+ state are determined. For the H2 isotopologue a three-laser scheme is employed yielding level energies at accuracies of 4×103 cm−1 for F(v=0,J) up to J=21 and for some low J values of F(v=1). A two-laser scheme was applied to determine level energies in H2 for F(v=04) levels as well as for various F levels in HD and D2, also up to large rotational quantum numbers. The latter measurements in the two-laser scheme are performed at lower resolution and the accuracy is strongly limited to 0.5 cm−1 by ac-Stark effects. For H2 a new quasibound resonance X1Σg+ (v=6, J=23) is detected through the Q(23) and O(23) transitions in the F0-X6 band. Also a quasi-bound resonance in D2 is assigned, for the first time in this species: X1Σg+ (v=17 , J=15). The experimental results on F(v,J) level energies are compared with previously reported theoretical results from multi-channel quantum-defect calculations as well as with results from newly performed non-adiabatic quantum calculations.

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来源期刊
CiteScore
2.70
自引率
21.40%
发文量
94
审稿时长
29 days
期刊介绍: The Journal of Molecular Spectroscopy presents experimental and theoretical articles on all subjects relevant to molecular spectroscopy and its modern applications. An international medium for the publication of some of the most significant research in the field, the Journal of Molecular Spectroscopy is an invaluable resource for astrophysicists, chemists, physicists, engineers, and others involved in molecular spectroscopy research and practice.
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High resolution laser diode spectroscopy of the hot bands of C2HD in the first overtone region of C-H stretching Buffer-gas cooling of hydrogen cyanide quantified by cavity-ringdown spectroscopy Pure rotational spectroscopic measurements on the electronic ground states of Hafnium monosulfide and Thorium monosulfide in highly excited vibrational states Isotopic species, vibrational states and nuclear quadrupole splitting in CH2Cl2 from rotational spectroscopy at 8–18 GHz Editorial Board
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