Quantitative simulations of electronically
nonadiabatic molecular
processes require both accurate dynamics algorithms and accurate electronic
structure information. Direct semiclassical nonadiabatic dynamics
is expensive due to the high cost of electronic structure calculations,
and hence it is limited to small systems, limited ensemble averaging,
ultrafast processes, and/or electronic structure methods that are
only semiquantitatively accurate. The cost of dynamics calculations
can be made manageable if analytic fits are made to the electronic
structure data, and such fits are most conveniently carried out in
a diabatic representation because the surfaces are smooth and the
couplings between states are smooth scalar functions. Diabatic representations,
unlike the adiabatic ones produced by most electronic structure methods,
are not unique, and finding suitable diabatic representations often
involves time-consuming nonsystematic diabatization steps. The biggest
drawback of using diabatic bases is that it can require large amounts
of effort to perform a globally consistent diabatization, and one
of our goals has been to develop methods to do this efficiently and
automatically. In this Feature Article, we introduce the mathematical
framework of diabatic representations, and we discuss diabatization
methods, including adiabatic-to-diabatic transformations and recent
progress toward the goal of automatization.
Multiconfiguration pair-density functional theory (MC-PDFT) has previously been applied successfully to carry out ground-state and excited-state calculations. However, because it includes no interaction between electronic states, MC-PDFT calculations in which...
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