We propose a coherent optical population transfer of weakly bound field-linked (FL) tetratomic molecules (tetramers) to deeper FL bound states using stimulated Raman adiabatic passage. We consider static-electric-field shielded polar alkali-metal diatomic molecules and corresponding FL tetramers in their X^{1}Σ^{+}+X^{1}Σ^{+} ground electronic state. We show that the excited metastable X^{1}Σ^{+}+b^{3}Π electronic manifold supports FL tetramers in a broader range of electric fields with collisional shielding extended to zero field. We calculate the Franck-Condon factors between the ground and excited FL tetramers and show that they are highly tunable with the electric field. We also predict photoassociation of ground-state shielded molecules to the excited FL states in free-bound optical transitions. We propose proof-of-principle experiments to implement stimulated Raman adiabatic passage and photoassociation using FL tetramers, paving the way for the formation of deeply bound ultracold polyatomic molecules.
The pure long-range
1u state of an alkali-metal dimer is observed in
39K2 using photoassociative spectroscopy of ultracold atoms. High-resolution spectra for vibrational levels $v=\stackrel{\ensuremath{\rightarrow}}{0}7$ are recorded by resonance-enhanced two-photon ionization. Strong rotation-hyperfine couplings are observed. Major molecular constants and a hyperfine structure analysis are presented. This
1u state is useful as an ungerade Franck-Condon ``window'' at large internuclear distance for studies of highly excited long-range interactions.