Splitting of the near infrared absorption bands of Sm in POCl3:SnCl4, POCl3:ZrCl4 and POCl3:TiCl4

The near infrared absorption spectra of Sm³⁺ in POCl₃:SnCl₄, POCl₃:ZrCl₄ and POCl₃:TiCl₄ consist of a series of bands, attributed to the ⁶H_5/2 → ⁶F_J transitions. Each one of these absorption bands is split into three components. The extent of splitting differs slightly from state to state. For each component of the ⁶F-multiplet the splitting decreases gradually from POCl₃:SnCl₄ to POCl₃:ZrCl₄ and POCl₃:TiCl₄. Energy differences between adjacent components of the near infrared absorption bands vary from a maximum of 166 cm⁻¹ to a minimum of 123 cm⁻¹. The band half-widths of the corresponding components vary from 86 to 120 cm⁻¹. At lower temperatures the intensity of the high energy component increases whereas the intensity of the entire absorption band envelope, associated with each component of the ⁶F-multiplet, remains almost constant. The splitting observed is attributed to the Stark splitting of the ⁶H_5/2-state of Sm³⁺ into three components, in conjunction with appropriate Stark splitting of the states of the ⁶F-multiplet.