%0 DATA
%A Xi-Chan, Gao
%A Qiang, Hao
%A Chang-Sheng, Wang
%D 2017
%T Improved Polarizable Dipole–Dipole Interaction
Model for Hydrogen Bonding, Stacking, T‑Shaped, and X–H···π
Interactions
%U https://acs.figshare.com/articles/Improved_Polarizable_Dipole_Dipole_Interaction_Model_for_Hydrogen_Bonding_Stacking_T_Shaped_and_X_H__Interactions/5026595
%R 10.1021/acs.jctc.6b00936.s001
%2 https://ndownloader.figshare.com/files/8489384
%K M 06-2X methods
%K SQM
%K overlap term
%K benchmark equilibrium
%K benchmark interaction energies
%K T-shaped
%K CCSD
%K polarization interaction term
%K nonpolarizable AMBER 99 force field method
%K RMSD
%K complex
%K M 06-2X
%K polarizable AMOEBA force field method
%K model
%X The
polarizable dipole–dipole
interaction model was formulated
in our laboratory to rapidly simulate hydrogen bonding in biosystems.
In this paper, this model is improved and further parametrized for
stacking, T-shaped, and X–H···π interactions
by adding the orbital overlap term and fitting to 19 CCSD(T)/CBS interaction
energy curves of training dimers. The performance of our model is
assessed through its application to more than 100 complexes, including
hydrogen-bonded, stacked, T-shaped, and X–H···π
complexes. For 124 relatively small testing complexes, our model reproduces
benchmark equilibrium intermolecular distances with a root-mean-square
deviation (RMSD) of 0.08 Å, and it reproduces benchmark interaction
energies with a 0.64 kcal/mol RMSD. For 14 large noncovalent complexes,
our model reproduces benchmark equilibrium intermolecular distances
with a RMSD of 0.05 Å, and it reproduces benchmark interaction
energies with a 0.80 kcal/mol RMSD. Extensive comparisons are made
to interaction energies calculated via the M06-2X and M06-2X-D3 methods,
via the well-known nonpolarizable AMBER99 force field method, via
the popular polarizable AMOEBA force field method, and via semiempirical
quantum mechanical (SQM) methods. Our statistical evaluations show
that our model outperforms the AMBER99, AMOEBA, and SQM methods and
is as accurate as the M06-2X and M06-2X-D3 methods. In summary, the
model developed in this work is reasonable, and the newly introduced
orbital overlap term is effective in the accurate modeling of the
noncovalent interactions. Our testing results also indicate that the
polarization interaction term is important in the evaluation of hydrogen
bonding, whereas the orbital overlap is important in examining short
hydrogen bonding, T-shaped, and X–H···π
interactions. Our model may serve as a new tool for modeling biological
systems where hydrogen bonding, stacking, T-shaped, and X–H···π
interactions are of general importance.