Separation of enantiomers by ultraviolet laser pulses in H2POSH: π pulses versus adiabatic transitions

Different strategies to separate enantiomers from a racemate using analytical laser pulses in the ultraviolet frequency domain are proposed for the prototype model system H2POSH. Wave-packet propagations on ab initio ground- and electronic-excited state potentials show that it is possible to produce 100% of enantiomeric excess in a sub-picosecond time scale using a sequence of π and half-π pulses. Alternatively, the previous transitions can be substituted by adiabatic counterparts, using chirped laser pulses and a half-STIRAP (stimulated Raman adiabatic passage) method which only transfers half of the population between appropriate levels. Such an overall adiabatic mechanism gains stability concerning the pulse areas and frequencies at the expense of introducing new control variables, like the chirp and time delay.