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本文推导了BrF振动基态(X 1Σ, v= 0)下 J= 1←0的转动超精细光谱的跃迁偶极矩, 总结了跃迁选择定则为: Δ J= ±1; Δ F 1= 0, ±1和Δ F= 0, ±1; 而且, 当Δ F 1= Δ F时谱线强度很强, 反之很弱. 当能级之间存在微扰相互作用时, 某些谱线由电偶极和核磁偶极跃迁共同产生, 然而磁偶极仅仅贡献大约十亿分之一的光谱强度. 计算所得光谱线宽和相对强度与实验结果一致. 同时, 在| JI 1 F 1 I 2 F
$\rangle $ 基矢下对Hamilton量矩阵对角化确定了转动超精细光谱的位置, 与实验误差小于1/50谱线宽度(<10 –8). 最后模拟了微波转动超精细光谱, 所得结果有助于超精细分子光谱实验和其他相关应用研究.The transition dipole of the hyperfine-rotation spectrum of J= 1←0 within the vibronic ground (X 1Σ, v= 0) state of BrF molecule is derived, and thus, the transition selection rules are summarized as follows: Δ J =±1; Δ F 1= 0, ±1 and Δ F= 0, ±1, and those of Δ F 1= Δ Fare intense while those of Δ F 1≠ Δ Fare weak. Some spectral lines result from both the electric dipole transition and nuclear magnetic dipole transition due to perturbations, however, the magnetic dipole transition only contributes about one-billionth in the spectral intensity. The spectral linewidth is determined to be about 18 kHz by calculating the spectral transition probability. The obtained spectral linewidth and relative intensities are consistent with the experimental results. Additionally, the hyperfine-rotation spectral positions are determined by diagonalizing the Hamiltonian matrix in the basis of | JI 1 F 1 I 2 F$\rangle $ , which is also in good agreement with the experiments within 10 –8(one-fiftieth of the spectral line width). Hence, the microwave hyperfine-rotation spectrum is simulated. In addition, we find that the nuclear spin-spin interaction not only slightly shifts the hyperfine-rotation spectral positions but also changes the sequence of the spectra. As to those unavailable constants of molecules, the fairly precise molecular constants can be achieved by quantum chemical calculation, say, by employing MOLPRO program, and then the simulated spectra can guide the spectral assignment. Besides the guidance of spectral assignment, our results are also helpful for other relevant applications such as in absolute single quantum state preparation.[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] -
79BrF 81BrF B/MHz 10628.46302 10577.63957 D/kHz 12.028 11.956 eqQ/MHz 1086.89197 907.97681 C1/kHz 89.051 95.818 C2/kHz –24.17 –24.54 C3/kHz –7.15 –7.71 C4/kHz 4.86 5.24 
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$F_1',F'\text{-}F''_1,F'' $ 79BrF 81BrF 强度
(归一化)计算值 误差a 计算值 误差a 0.5, 0–1.5, 1 20986.0744 0.0003 20928.7933 0 0.1428 0.5, 1–1.5, 1 20986.1035 –0.0011 20928.8236 0.0002 0.0917 1.5, 1–1.5, 1 21475.0918 0 21337.3854 0.0001 0.3571 1.5, 2–1.5, 1 21475.0730 21337.3660 0.0713 2.5, 2–1.5, 1 21203.1734 0.0001 21110.3358 0 0.6427 0.5, 1–1.5, 2 20986.0937 0 20928.8131 –0.0002 0.3570 1.5, 1–1.5, 2 21475.0820 21337.3749 0.0714 1.5, 2–1.5, 2 21475.0632 0 21337.3556 –0.0001 0.6427 2.5, 2–1.5, 2 21203.1636 21110.3253 0.0713 2.5, 3–1.5, 2 21203.1484 0 21110.3109 0 1 σb 0.0004 0.0001 a计算值减去参考文献中的实验值[37], 误差缺失表示谱线强度太弱而实验无法观测到. bσ为计算总体方差. 下载:
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$ (J' = 1)F_1', F' $ $(J'' = 0) F_1'', F''$ 0.5, 0 0.5, 1 1.5, 1 1.5, 2 2.5, 2 2.5, 3 1.5, 1 0.2247 0.1124 0.5616 0.1123 1.0110 0 1.5, 2 0 0.5617 0.1123 1.0110 0.1122 1.5728 下载:
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