Chapter 14
Full and Ab Initio Multiple Spawning
Basile F. E. Curchod,
Basile F. E. Curchod
Department of Chemistry, Durham University, Durham, DH1 3LE United Kingdom
Search for more papers by this authorBasile F. E. Curchod,
Basile F. E. Curchod
Department of Chemistry, Durham University, Durham, DH1 3LE United Kingdom
Search for more papers by this authorBook Editor(s):Leticia González,
Roland Lindh,
Leticia González
Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Austria
Search for more papers by this authorRoland Lindh
Department of Chemistry – BMC, Uppsala University, Sweden
Search for more papers by this authorSummary
This Chapter describes the method for non-adiabatic quantum molecular dynamics called Full Multiple Spawning. The Full Multiple Spawning framework proposes to portray nuclear wave functions by linear combinations of classically-traveling multi-dimensional Gaussian functions, called trajectory basis functions. The number of trajectory basis functions can be adapted when needed during the excited-state dynamics through a spawning algorithm, and all basis functions are coupled together.
Hence, Full Multiple Spawning is a formally exact method for non-adiabatic dynamics in the limit of a large number of basis functions. Full Multiple Spawning can be extended to the description of light/matter interaction or the inclusion of spin-orbit coupling effects. Two controlled approximations can be performed on the Full Multiple Spawning equations and lead to the Ab Initio Multiple Spawning technique, which allows for on-the-fly non-adiabatic quantum dynamics of medium-size molecules. In addition to describing the formalism and algorithms of the Full- and Ab Initio Multiple Spawning, this Chapter presents a dissection of a typical Ab Initio Multiple Spawning dynamics run, as well as different successful applications of this technique.
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