Preparation of a selected high vibrational energy level of isolated molecules

Stark induced adiabatic Raman passage (SARP) allows us to prepare an appreciable concentration of isolated molecules in a specific, high-lying vibrational level. The process has general applicability, and, as a demonstration, we transfer nearly 100 percent of the HD (v = 0, J = 0) in a supersonically expanded molecular beam of HD molecules to HD (v = 4, J = 0). This is achieved with a sequence of partially overlapping nanosecond pump (355 nm) and Stokes (680 nm) single-mode laser pulses of unequal intensities. By comparing our experimental data with our theoretical calculations, we are able to draw two important conclusions: (1) using SARP a large population (>10¹⁰ molecules per laser pulse) is prepared in the (v = 4, J = 0) level of HD and (2) the polarizability α_00,40 (≅0.6 × 10^-41 C m² V^-1) for the (v = 0, J = 0) to (v = 4, J = 0) Raman overtone transition is only about five times smaller than α_00,10 for the (v = 0, J = 0) to (v = 1, J = 0) fundamental Raman transition. Moreover, the SARP process selects a specific rotational level in the vibrational manifold and can prepare one or a phased linear combination of magnetic sublevels (M states) within the selected vibrational-rotational level. This capability of preparing selected, highly excited vibrational levels of molecules under collision-free conditions opens new opportunities for fundamental scattering experiments.