Abstract
The vibration-induced permanent dipole moments in SiH4 and in SiF4 have been determined by measuring the first-order Stark effect on the infrared vibration–rotation lines in the triply degenerate ν4 and ν3 fundamental bands, respectively. Microwave modulation sidebands on CO2 laser lines were generated with sufficient power and spectral purity to be used as the frequency-tunable infrared source for the sub-Doppler saturation Lamb dip measurements. Theory is also presented for calculating the dipole moment matrix elements in the excited vibrational state. From the observed Stark splittings, the vibration-induced permanent dipole moment P has been determined to be 1.46(5)×10−2 D for SiH4 in the v4=1 state, and 4.21(12)×10−2 D for SiF4 in the v3=1 state. In addition, Watson’s coefficient for the rotation-induced permanent dipole moment θxyz has been determined to be 2.97(19)×10−5 D in SiH4 (v4=1).
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