@article{8e674165c8004b53b2da14a1239dfcdf,
title = "The permanent electric dipole moment of calcium monodeuteride",
abstract = "The sub-Doppler laser induced fluorescence spectra of numerous branch features in the B +2 -X +2 (0,0) band of calcium monodeuteride were recorded field-free and in the presence of a static electric field of up to 7 kVcm. The field-free spectra were analyzed to produce an improved set of fine structure parameters for the B +2 (v=0) state. The observed electric field induced splittings and shifts were analyzed to produce permanent electric dipole moments of 2.57(3) and 2.51 (3) D for B +2 (v=0) and X +2 (v=0) states, respectively. The permanent electric dipole moment for the X +2 (v=0) state of CaH is estimated to be 2.53 (3) D.",
author = "Jinhai Chen and Timothy Steimle",
note = "Funding Information: This research has been supported in part by the National Science Foundation—Experimental Physical Chemistry (Grant No. 0646473). Table I. The observed and calculated transition wavenumber ( cm − 1 ) for the field-free B Σ + 2 − X Σ + 2 ( 0 , 0 ) band of CaD. Branch J ″ Observed Obs. − Calc. Fit A a Fit B b Q 12 P 3 ∕ 2 15 744.5495 0.0017 − 0.0109 5 ∕ 2 15 740.1743 0.0039 − 0.0025 7 ∕ 2 15 735.9630 − 0.0045 0.0008 P 11 P 3 ∕ 2 15 744.5160 0.0018 − 0.0108 5 ∕ 2 15 740.1174 0.0030 − 0.0034 7 ∕ 2 15 735.8828 − 0.0062 − 0.0010 P 22 P 5 ∕ 2 15 740.7819 − 0.0046 − 0.0063 R 11 R 1 ∕ 2 15 753.2023 0.0056 − 0.0008 3 ∕ 2 15 757.6813 0.0072 0.0125 5 ∕ 2 15 762.3177 − 0.0005 0.0150 R 11 R 7 ∕ 2 15 767.1125 − 0.0081 0.0054 9 ∕ 2 15 772.0732 0.0046 − 0.0113 Q 21 R 1 ∕ 2 15 753.8062 − 0.0066 − 0.0083 3 ∕ 2 15 758.6735 − 0.0097 − 0.0012 5 ∕ 2 15 763.7106 0.0170 0.0275 7 ∕ 2 15 768.8194 − 0.0054 − 0.0149 R 22 R 3 ∕ 2 15 758.7074 − 0.0094 − 0.0009 5 ∕ 2 15 763.7667 0.0171 0.0276 7 ∕ 2 15 768.8963 − 0.0070 − 0.0165 a Standard deviation of Fit A = 0.0078 cm − 1 . b Standard deviation of Fit B = 0.0124 cm − 1 . Table II. Observed and calculated Stark shifts for the lines of the B Σ + 2 − X Σ + 2 ( 0 , 0 ) transition of CaD. Branch Field(V/cm) ∣ M J ′ ∣ ∣ M J ″ ∣ Obs(MHz) Dif(MHz) Q 21 R ( 0.5 ) 1851 1 ∕ 2 1 ∕ 2 18 4 ∥ 3629 1 ∕ 2 1 ∕ 2 39 − 13 4295 1 ∕ 2 1 ∕ 2 86 13 5110 1 ∕ 2 1 ∕ 2 103 − 1 Q 21 R ( 0.5 ) 1851 1 ∕ 2 1 ∕ 2 17 3 ⊥ 3746 1 ∕ 2 1 ∕ 2 52 − 4 4400 1 ∕ 2 1 ∕ 2 105 18 5110 1 ∕ 2 1 ∕ 2 112 8 5739 1 ∕ 2 1 ∕ 2 144 13 6368 1 ∕ 2 1 ∕ 2 183 16 R 11 R ( 0.5 ) 1851 1 ∕ 2 1 ∕ 2 22 4 ∥ 3747 1 ∕ 2 1 ∕ 2 79 3 4202 1 ∕ 2 1 ∕ 2 104 9 4943 1 ∕ 2 1 ∕ 2 135 3 R 11 R ( 0.5 ) 5739 3 ∕ 2 1 ∕ 2 81 − 12 ⊥ 5739 1 ∕ 2 1 ∕ 2 162 − 16 6368 3 ∕ 2 1 ∕ 2 107 − 8 6368 1 ∕ 2 1 ∕ 2 209 − 9 7010 3 ∕ 2 1 ∕ 2 134 − 5 7010 1 ∕ 2 1 ∕ 2 266 1 P 11 P ( 1.5 ) 1851 1 ∕ 2 1 ∕ 2 − 6 12 ∥ 3733 1 ∕ 2 1 ∕ 2 − 85 − 10 4375 1 ∕ 2 1 ∕ 2 − 96 7 5122 1 ∕ 2 1 ∕ 2 − 1.37 5 P 11 P ( 1.5 ) 5085 1 ∕ 2 3 ∕ 2 − 81 − 6 ⊥ 5085 1 ∕ 2 1 ∕ 2 − 135 5 5609 1 ∕ 2 3 ∕ 2 − 96 − 4 5609 1 ∕ 2 1 ∕ 2 − 174 − 5 6405 1 ∕ 2 3 ∕ 2 − 114 5 6405 1 ∕ 2 1 ∕ 2 − 215 9 7047 1 ∕ 2 3 ∕ 2 − 145 − 1 7047 1 ∕ 2 1 ∕ 2 − 275 − 4 Q 12 P ( 1.5 ) 1851 1 ∕ 2 1 ∕ 2 − 7 7 ∥ 3740 1 ∕ 2 1 ∕ 2 − 46 11 4369 1 ∕ 2 1 ∕ 2 − 80 − 2 5134 1 ∕ 2 1 ∕ 2 − 103 4 Q 12 P ( 1.5 ) 1851 1 ∕ 2 1 ∕ 2 − 23 − 9 ⊥ 3759 1 ∕ 2 1 ∕ 2 − 56 2 4394 1 ∕ 2 1 ∕ 2 − 82 − 3 5054 1 ∕ 2 1 ∕ 2 − 101 3 5739 1 ∕ 2 1 ∕ 2 − 129 4 6374 1 ∕ 2 1 ∕ 2 − 173 − 10 7034 1 ∕ 2 1 ∕ 2 − 200 − 2 Table III. The determined B Σ + 2 state spectroscopic parameters ( cm − 1 ) from the analysis of the field-free B Σ + 2 − X Σ + 2 ( 0 , 0 ) band system of CaD. Parameters Fit A Fit B Ref. 17 B 0 2.2619(14) 2.2577(6) 2.256(6) D 0 2.2 ( 6 ) × 10 − 4 5.32 × 10 − 5 a 5.32 ( 55 ) × 10 − 5 γ − 0.4143 ( 50 ) − 0.4103 ( 73 ) − 0.409 ( 7 ) γ D 0.0018(3) 0.0013(4) ⋯ T 0 15 748.8791(62) 15 748.8791(71) ⋯ a Constrained to value determine in Ref. 17 . Table IV. Permanent electric dipole moments (D) of CaD and CaH. State CaD CaH Ab initio Expt. a Ab initio Expt. a X Σ + 2 2.575, c 2.614 d 2.51(3) 2.46, e 2.58, f 2.68, g 2.32, h 2.617, j 2.623 b 2.94(16) i 2.53(3) k A Π 2 2.499 c 2.36, d 2.368 l 2.372(12) f B Σ + 2 2.750 c 2.57(3) 2.39, d 2.871 l a The numbers in parentheses represent a purely statistical 1 σ error estimate. The systematic error is estimated to be 2% CaD values from this work. b Reference 3 at R e . c Reference 23 at R 0 . d Reference 24 at R 0 . e Reference 10 at R c . f Reference 12 at R e . g Reference 13 at R e . h Reference 2 at R e . i Reference for v = 0 . j Reference 3 at R 0 . k From CaD value and theoretical value for Δ μ ∕ Δ R of Ref. 3 . l Reference 3 at R e . FIG. 1. The field free LIF spectrum of the X Σ + 2 − B Σ + 2 ( 0 , 0 ) band of CaD in the region of the R 11 R ( 0.5 ) and associated satellite Q 21 R ( 0.5 ) branch features; the sub-Doppler I 2 absorption spectrum and the transmission of an actively stabilized confocal {\'e}talon. FIG. 2. The field-free and Stark spectra of the R 11 R ( 0.5 ) line (left hand panel) and the associated energy level as a function of applied electric field (right hand panel). The electric field of the radiation was perpendicular to the static electric field, giving Δ M J = ± 1 transitions. ",
year = "2008",
doi = "10.1063/1.2899651",
language = "English (US)",
volume = "128",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "14",
}