The

Difficulties of Calculating Stacking Energy on Covalent System

Non-covalent interactions play important roles in various condense matters and

bio-molecular system. Complex structures of bio-molecules are generally constructed
from fundamental subunits that bind together by intermolecular interaction. Hydrogen
bonding and dispersion interactions are a type of non-covalent interaction taking a
dominant effect in biomolecules. It is widely known that non-covalent interactions have
been a major problem in quantum chemistry (QC) because its difficulty to capture the
correlation effects, especially dispersion interactions. Unlike hydrogen bond, dispersion
interactions can not be treated by Hartree-Fock (HF) or even density functional theory
(DFT) with conventional exchange-correlation (XC) functional. In order to overcome this
problem, several methods based on DFT have been developed to invent the new XC
functional. Dispersion-corrected DFT (DFT-D) is the well-known XC for treating dispersion.
But, in some literatures, it was said that DFT-D still fail to capture dispersion in
biomolecules such as B-DNA even though most of them agree with experimental or
higher-level ab initio methods. These conclusions result in inaccurate non additive
interaction driven by dispersion. On the other hand, second-order MØller-Plesset
perturbation theory (MP2) is believed as the cheapest approximation for dynamical
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electron correlation with computational cost N where N is number of electrons of the
system, however, one the serious short-coming of MP2 method is noticeable over-bind of
dispersion interaction which plays an important role for the stability and formation. At the
present, coupled-cluster with single and double excitations including non-iterative triples
(CCSD(T)) is accepted as “golden standard” to provide more accurate dispersion
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interaction but only applicable in small system because of its scaling behavior N .
Recently, Quantum Monte Carlo has successful in treating small and big biomolecules
including non additive interaction and more favorable scaling behavior N , it is also known
that fixed-node diffusion Monte Carlo (DMC) provides the most accurate and practical
QMC methods moreover believed as the most accurate methods compared to another
methods such DFT or HF. Thus, our hypnotize is DMC’s result for calculating non additive
energy in non-covalent system is almost similar with CCSD(T)/CBS and has different result
from MP3, MP4 as well as DFT-D. In order to prove it, we try to investigate it by using
small system because its interactions are held by dispersion (no hydrogen bond) and
cheap computational cost.