Non-adiabatic Thouless pumping of
electrons is studied in the framework
of topological Floquet engineering, particularly with a focus on how
atomistic changes to chemical moieties control the emergence of the
Floquet topological phase. We employ real-time time-dependent density
functional theory to investigate the extent to which the topological
invariant, the winding number, is impacted by molecular-level changes
to trans-polyacetylene. In particular, several substitutions
to trans-polyacetylene are studied to examine different
effects on the electronic structure, including the mesomeric effect,
inductive effect, and electron conjugation effect. Maximally localized
Wannier functions are employed to relate the winding number to the
valence bond description by expressing the topological pumping as
the transport dynamics of the localized Wannier functions. By further
exploiting the gauge invariance of the quantum dynamics in terms of
the minimal particle–hole excitations, the topological pumping
of electrons can be also represented as a cyclic transition among
the bonding and antibonding orbitals. Having connected the topological
invariant to the chemical concepts, we demonstrate molecular-level
control of the emergence of the Floquet topological phase, presenting
an exciting opportunity for the intuitive engineering of molecular
systems with such an exotic topological phase.