posted on 2023-11-21, 17:36authored byHengyuan Shen, Srimukh Prasad Veccham, Martin Head-Gordon
Energy decomposition analysis (EDA)
is a useful method
to unravel
intermolecular interaction energy into chemically meaningful components
such as geometric distortion, frozen interactions, polarization, and
charge transfer. A further decomposition of the polarization (POL)
and charge transfer (CT) energy into fragment-wise contributions would
be useful to understand the significance of each fragment during these
two processes. To complement the existing exact pairwise decomposition
of the CT term, this work describes the formulation and implementation
of a nonperturbative polarization analysis that decomposes the POL
energy into an exactly fragment-wise additive sum based on the absolutely
localized molecular orbital energy decomposition analysis (ALMO-EDA).
These fragment-wise contributions can be further decomposed into chemically
intuitive molecular orbital pairs using complementary occupied-virtual
pair (COVP) analysis. A very useful phase convention is established
for each COVP such that constructive interference of occupied and
virtual corresponds to electron flow into that region, while destructive
interference corresponds to electron outflow. A range of model problems
are used to demonstrate that the polarization process is typically
a collective behavior of the electrons that is quite different from
the charge transfer process. This provides another reason in addition
to their different distance dependence on fragment separation for
separating these two processes in EDA.