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Review of the hyperfine structure theory of hydrogen molecular ions

Zhong Zhen-Xiang

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Review of the hyperfine structure theory of hydrogen molecular ions

Zhong Zhen-Xiang
cstr: 32037.14.aps.73.20241101
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  • The study of high-precision spectroscopy for hydrogen molecular ions enables the determination of fundamental constants, such as the proton-to-electron mass ratio, the deuteron-to-electron mass ratio, the Rydberg constant, and the charge radii of proton and deuteron. This can be accomplished through a combination of high precision experimental measurements and theoretical calculations. The spectroscopy of hydrogen molecular ions reveals abundant hyperfine splittings, necessitating not only an understanding of rovibrational transition frequencies but also a thorough grasp of hyperfine structure theory to extract meaningful physical information from the spectra. This article reviews the history of experiments and theories related to the spectroscopy of hydrogen molecular ions, with a particular focus on the theory of hyperfine structure. As far back as the second half of the last century, the hyperfine structure of hydrogen molecular ions was described by a comprehensive theory based on its leading-order term, known as the Breit-Pauli Hamiltonian. Thanks to the advancements in non-relativistic quantum electrodynamics (NRQED) at the beginning of this century, a systematic development of next-to-leading-order theory for hyperfine structure has been achieved and applied to $\text{H}_2^+$ and $\text{HD}^+$ in recent years, including the establishment of the $m\alpha^7\ln(\alpha)$ order correction. For the hyperfine structure of $\text{H}_2^+$, theoretical calculations show good agreement with experimental measurements after decades of work. However, for HD+, discrepancies have been observed between measurements and theoretical predictions that cannot be accounted for by the theoretical uncertainty in the non-logarithmic term of the $m\alpha^7$ order correction. To address this issue, additional experimental measurements are needed for mutual validation, as well as independent tests of the theory, particularly regarding the non-logarithmic term of the $m\alpha^7$ order correction.
      Corresponding author: Zhong Zhen-Xiang, zxzhong@hainanu.edu.cn
    • Funds: Project supported by the Key Program of the National Natural Science Foundation of China (Grant No. 12393821) and the National Key Research and Development Program of China (Grant No. 2021YFA1402103).
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  • 图 1  氢分子离子$ \text{H}_2^+ $振转态$ (v, L=1, 3) $的超精细劈裂示意图

    Figure 1.  Hyperfine structure of hydrogen molecular ion $ \text{H}_2^+ $ rovibrational states $ (v, L=1, 3) $.

    图 2  氢分子离子HD+振转态$ (v, L\geqslant2) $的超精细劈裂示意图

    Figure 2.  Hyperfine structure of hydrogen molecular ion HD+ rovibrational states $ (v, L\geqslant2) $.

    表 1  通过氢分子离子精密光谱测定质子-电子质量比

    Table 1.  Determination of the proton-electron mass ratio through precision spectroscopy of hydrogen molecular ions.

    年份 作者(研究机构) 跃迁$ (v, L)\rightarrow (v', L') $ 所测频率/MHz 理论频率/MHz 质量比
    HD+
    2007 Koelemeij
    et al. (HHU)[16]
    $ (0, 2)\rightarrow (4, 3) $ 214978560.6(0.5) 214978560.88(7)[62]
    2016 Biesheuvel
    et al. (VU)[18]
    $ (0, 2)\rightarrow (8, 3) $ 383407177.38(41) 383407177.150(15)[20] 1836.1526695(53)
    2018 Alighanbari
    et al. (HHU)[63]
    $ (0, 0)_{J=2}\rightarrow (0, 1)_{J'=3} $ 1314935.8280(4)(3)a 1314935.8273(10)b 1836.1526739(24)
    2020 Alighanbari
    et al. (HHU)[23]
    $ (0, 0)\rightarrow (0, 1) $ 1314925.752910(17) 1314925.752896(18)(61)b,c 1836.152673449(24)
    (25)(13)d
    2020 Patra
    et al. (VU)[24]
    $ (4, 2)\rightarrow (9, 3) $ 415264925.5005(12) 415264925.4962(74)b 1836.152673406(38)
    2021 Kortunov
    et al. (HHU)[64]
    $ (0, 0)\rightarrow (1, 1) $ 58605052.16424(16)(85)e 58605052.1639(5)(13)b,c 1836.152673384(11)
    (31)(55)(12)f
    2023 Alighanbari
    et al. (HHU)[17]
    $ (0, 0)\rightarrow (5, 1) $ 259762971.0512(6)
    (0.00004)e
    259762971.05091[41] 1836.152673463
    (10)(35)(1)(6)f
    $ \text{H}_2^+ $
    2024 Schenkel
    et al. (HHU)[65]
    $ (1, 0)\rightarrow (3, 2) $ 124487032.7(1.5) 124487032.45(6) [40] 1836.152665(53)
    CODATA推荐值
    2014 CODATA group[66] CODATA 2014 1836.15267389(17)
    2018 CODATA group[22] CODATA 2018 1836.15267343(11)
    2022 CODATA groupg CODATA 2022 1836.152673426(32)
    注: a 第一个误差为统计误差, 第二个为系统误差; b 来自Korobov, 是该实验文章的共同作者; c 第一个误差来自理论, 第二个来自CODATAk 2018基本物理常数; d 第一个误差来自实验, 第二个来自理论, 第三个来自CODATAk 2018基本物理常数; e 第一个误差来自实验, 第二个来自超精细结构理论; f 第一个误差来自实验, 第二个来自QED理论, 第三个来自超精细结构理论, 第四个来自CODATA 2018基本物理常数; g 来自NIST的基本物理常数表https://physics.nist.gov/cuu/Constants/index.html.
    DownLoad: CSV

    表 2  基于HD+中不同的振转跃迁测量定出的质量比组合$ \mathcal{R}$之比较[17]

    Table 2.  Comparison of the combined mass ratio $\mathcal{R}$ determined from the measurements of different rovibrational transitions in HD+ [17].

    年份 振转跃迁 $ \mathcal{R} $ 相对误差 引文
    2020 $ (0, 0)\rightarrow (0, 1) $ 1223.899228658(23) $ 1.9\times10^{-11} $ HHU[23]
    2020 $ (0, 3)\rightarrow (9, 3) $ 1223.899228735(28) $ 2.3\times10^{-11} $ VU[67]
    2021 $ (0, 0)\rightarrow (0, 1) $ 1223.899228711(22) $ 1.8\times10^{-11} $ HHU[64]
    2023 $ (0, 0)\rightarrow (5, 1) $ 1223.899228720(25) $ 2.0\times10^{-11} $ HHU[17]
    1223.899228642(37) $ 3.0\times10^{-11} $ 潘宁阱[25,26,68]
    1223.899228723(56) $ 4.8\times10^{-11} $ CODATA 2018[22]
    DownLoad: CSV

    表 3  $ \text{H}_2^+ $等效哈密顿量(9)中的超精细劈裂系数, 单位为kHz. 每个振转态的第一行是理论值, 随后是实验值. d1d2需要乘以因子$ 3(2 L-1)(2 L+3) $才能与文献[51]中的值匹配

    Table 3.  The hyperfine splitting coefficients in the effective Hamiltonian of $ \text{H}_2^+ $, as appeared in Eq. (9), in units of kHz. The first line of each rovibrational state is for the theoretical values, followed by the experimental ones. d1 and d2 need to be multiplied by $ 3(2 L-1)(2 L+3) $ to match the values in Ref. [51].

    L v bF ce cI d1 d2
    1 0 922 930.1(9)a 42 417.32(15)b –41.673d 8566.174(17)b –19.837d
    922 940(20)[53] 42 348(29)[53] –3(15)[53] 8550.6(1.7)[53]
    923.16(21)[54]
    1 4 836 728.7(8)a 32 655.32(11)b –35.826c 6537.386(13)b –16.414c
    836 729.2(8)[52] 32 636[52] –34(1.5)e 6535.6[52]
    1 5 819 226.7(8)a 30 437.80(11)b –34.148c 6080.400(12)b –15.531c
    819 227.3(8)[52] 30 421[52] –33(1.5)e 6078.7[52]
    1 6 803 174.5(7)a 28 280.95(10)b –32.385c 5637.627(11)b –14.633c
    803 175.1(8)[52] 28 266[52] –31(1.5)e 5636.0[52]
    1 7 788 507.5(7)a
    788 507.9(8)[52] 26 156[52] –29(1.5)e 5204.9[52]
    1 8 775 171.2(7)a
    775 172.0(8)[52] 24 080[52] –27(1.5)e 4782.2[52]
    注: a 包含高阶修正的贡献, 来自文献[49]; b 包含高阶修正的贡献, 来自文献[59]; c 仅计算领头项$ m\alpha^4 $阶的Breit-Pauli哈密顿量的贡献, 误差为相应值乘以$ \alpha^2\approx5.3\times10^{-5} $, 来自文献[51]; d 仅计算领头项$ m\alpha^4 $阶的Breit-Pauli哈密顿量的贡献, 误差为相应值乘以$ \alpha^2\approx5.3\times10^{-5} $, 来自文献[30]; e 由Babb于1995年重新拟合实验数据获得, 来自文献[46].
    DownLoad: CSV

    表 4  $ \text{H}_2^+ $在特定的转动量子数L下, 可能具有的不同总自旋量子数F和总角动量量子数J的值. n是相应的超精细劈裂态的数目, 见文献[93]表I

    Table 4.  Possible values of different total spin quantum number F and total angular momentum quantum number J that $ \text{H}_2^+ $ may have under specific rotational quantum number L. n is the number of corresponding hyperfine splitting states, see Table I in Ref. [93].

    L se I F J n
    0 1/2 0 1/2 1/2 1
    1 1/2 1 1/2 1/2, 3/2 5
    3/2 1/2, 3/2, 5/2
    1/2 0 1/2 $ L-1/2, L+1/2 $ 2
    1/2 1 1/2 $ L-1/2, L+1/2 $ 6
    3/2 $ L-3/2, L-1/2, L+1/2, L+3/2 $
    DownLoad: CSV

    表 5  $ \text{H}_2^+ $在振转态$ (v=4—8, L=1) $下, 超精细劈裂态$ (F, J) $之间的跃迁频率理论和实验结果比较, 单位为MHz. 第一行是Korobov等[58]计算的理论值; 第二行中的实验值来源于文献[52]. 对于$ v=4—6 $的跃迁$ (1/2, 3/2)—(1/2, 1/2) $, 理论值已于2022年得到更新[59], 相应的实验值取自引文[94]

    Table 5.  Comparison of theoretical and experimental transition frequencies between hyperfine states of $ \text{H}_2^+ $ in rovibrational state $ (v=4—8, L=1) $, in MHz. The first row shows the theoretical values calculated by Korobov et al.[58]; the experimental values in the second row are from the Ref. [52]. For transitions $ (F, J)=(1/2, 3/2)—(1/2, 1/2) $ for $ v=4—6 $, the theoretical values were updated in 2022[59], and the corresponding experimental values are cited from Ref. [94].

    v $ \left(\dfrac{3}{2}, \dfrac{3}{2}\right)—\left(\dfrac{3}{2}, \dfrac{5}{2}\right) $ $ \left(\dfrac{3}{2}, \dfrac{3}{2}\right)—\left(\dfrac{3}{2}, \dfrac{1}{2}\right) $ $ \left(\dfrac{1}{2}, \dfrac{3}{2}\right)—\left(\dfrac{1}{2}, \dfrac{1}{2}\right) $ $ \left(\dfrac{3}{2}, \dfrac{5}{2}\right)—\left(\dfrac{1}{2}, \dfrac{3}{2}\right) $ $ \left(\dfrac{3}{2}, \dfrac{3}{2}\right)—\left(\dfrac{1}{2}, \dfrac{3}{2}\right) $
    4 5.7202 74.0249 15.371316(56)a 1270.5504 1276.2706
    5.721 74.027 15.371407(2)b 1270.550 1276.271
    5 5.2576 68.9314 14.381453(52)a 1243.2508 1248.5084
    5.258 68.933 14.381513(2)b 1243.251 1248.509
    6 4.8168 63.9879 13.413397(48)a 1218.1538 1222.9706
    4.817 63.989 13.413460(2)b 1218.154 1222.971
    7 4.3948 59.1626 12.4607 1195.1558 1199.5506
    4.395 59.164 12.461 1195.156 1199.551
    8 3.9892 54.4238 11.5172 1174.1683 1178.1576
    3.989 54.425 11.517 1174.169 1178.159
    注: a 来自引文[59]的理论值; b 来自引文[94]的实验值.
    DownLoad: CSV

    表 6  实验涉及的HD+振转态超精细劈裂系数, 单位kHz. 振转态(0, 1)的系数E1, E6E7实验值 (第二个条目) 由Haidar等[50]从实验数据[23]中提取

    Table 6.  Hyperfine coefficients for rovibrational states of HD+, in kHz. Experimental values (the second entry) of coefficients E1, E6 and E7 for rovibrational state (0, 1) were extracted by Haidar et al. in Ref. [50] from experimental data[23].

    (v, L) (0, 0) (0, 1) (1, 1) (6, 1) (0, 3) (9, 3)
    E1[50] 31985.41(12) 30280.74(11) 22643.89(8) 31628.10(11) 18270.85(6)
    31984.9(1)
    E2[47] –31.345(8) –30.463(8) –25.356(7) –30.832(8) –21.304(6)
    E3[47] –4.809(1) –4.664(1) –3.850(1)a –4.733(1) –3.225(1)
    E4[49] 925394.2(9) 924567.7(9) 903366.5(8) 816716.1(8) 920480.0(9) 775706.1(7)
    E5[49] 142287.56(8) 142160.67(8) 138910.27(8) 125655.51(7) 141533.07(8) 119431.93(7)
    E6[50] 8611.299(18) 8136.859(17) 6027.925(13) 948.5421(20) 538.9991(12)
    8611.17(5)
    E7[50] 1321.7960(28) 1248.9624(27) 925.2072(20) 145.5969(3) 82.7250(2)
    1321.72(4)
    E8[47] –3.057(1) –2.945(1) –2.369(1)a –0.335 –0.219
    E9[50] 5.660(1) 5.653(1) 5.204(1)a 0.612 0.501
    注: a 未见于文献中, 由本文作者计算.
    DownLoad: CSV

    表 7  HD+振转态(v, L)可能具有的总自旋角动量F和总角动量J的值

    Table 7.  Possible total spin angular momentum F and total angular momentum J values for HD+ rotational state (v, L).

    L F S J
    L 0 1 $ L-1, L, L+1 $
    1 0 L
    1 $ L-1, L, L+1 $
    2 $ L-2, L-1, L, L+1, L+2 $
    DownLoad: CSV

    表 8  HD+超精细劈裂跃迁频率fij的理论值和实验值比较, 单位kHz. $ f_{ij}=f_j-f_i $, 这里fi是振转跃迁$ (v, L)\rightarrow (v', L') $光谱的第i个超精细劈裂峰, 参考实验文献[23, 24, 64]. $ \varDelta_{ij}=f_{ij}^\text{exp}-f_{ij}^\text{theor} $是实验与理论之间的偏差, $ \sigma_{\mathrm{c}}=\{[u(f_{ij}^\text{exp})]^2+ $$ [u(f_{ij}^\text{theor})]^2\}^{1/2} $是实验与理论值之间的标准误差, 这里$ u(f) $表示f的相对误差

    Table 8.  Comparison between experimental and theoretical results for some hyperfine intervals, in kHz. $ f_{ij}=f_j-f_i $, where fi is the i-th hyperfine component of rovibrational transition $ (v, L)\rightarrow (v', L') $, see Refs. [23, 24, 64]. $ \varDelta_{ij}=f_{ij}^\text{exp}- $$ f_{ij}^\text{theor} $ is the deviation between experimental and theoretical frequencies, and $ \sigma_{\mathrm{c}}=\{[u(f_{ij}^\text{exp})]^2+[u(f_{ij}^\text{theor})]^2\}^{1/2} $ is the standard deviation, with $ u(f) $ being the relative uncertainty in f.

    i $ FSJ\rightarrow F'S'J' $ j $ FSJ\rightarrow F'S'J' $ $ f_{ij}^\text{exp} $ $ f_{ij}^\text{theor} $[50] $ \varDelta_{ij} $ $ \varDelta_{ij}/\sigma_c $
    $ (v=0, L=0)\longrightarrow(v'=0, L'=1) $ $ f_{ij}^\text{exp} $来自引文[23]
    12 122→121 14 100→101 2434.211(75) 2434.465(23) –0.254 –3.2
    12 122→121 16 011→012 31074.752(43) 31074.102(56) –0.350 –4.9
    12 122→121 19 122→123 43283.419(54) 43284.10(12) –0.677 –5.0
    12 122→121 20 122→122 44944.338(72) 44945.289(64) –0.951 –9.8
    12 122→121 21 111→112 44996.486(61) 44997.14(11) –0.652 –5.3
    14 100→101 16 011→012 6939.541(66) 6939.636(42) –0.095 –1.2
    14 100→101 19 122→123 1949.208(47) 1948.63(11) –0.423 –3.2
    14 100→101 20 122→122 20810.127(88) 20810.823(63) –0.696 –6.5
    14 100→101 21 111→112 20862.275(79) 20862.673(91) –0.398 –3.3
    16 011→012 19 122→123 12209.667(41) 12209.994(72) –0.327 –4.0
    16 011→012 20 122→122 13870.586(62) 13871.187(42) –0.601 –7.9
    16 011→012 21 111→112 13922.734(49) 13923.037(51) –0.303 –4.3
    19 122→123 20 122→122 1660.919(70) 1661.19(10) –0.274 –2.2
    19 122→123 21 111→112 1713.067(59) 1713.042(25) 0.025 0.4
    20 122→122 21 111→112 52.148(6) 51.850(75) 0.298 2.8
    $ (v=0, L=0)\longrightarrow(v'=1, L'=1) $ $ f_{ij}^\text{exp} $来自引文[64]
    12 122→121 16 122→123 41294.06(32) 41293.66(12) 0.40 1.2
    $ (v=0, L30)\longrightarrow(v'=9, L'=3) $ $ f_{ij}^\text{exp} $来自引文[24]
    $ F=0 $ 014→014 $ F=1 $ 125→125 178254.4(9) 178245.89(28) 8.5 9.0
    DownLoad: CSV
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  • Received Date:  06 August 2024
  • Accepted Date:  27 August 2024
  • Available Online:  26 September 2024
  • Published Online:  20 October 2024

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