Enabling Rapid and Accurate Construction of CCSD(T)-Level Potential Energy Surface of Large Molecules Using Molecular Tailoring Approach

The construction of a potential energy surface (PES) of even a
medium-sized molecule employing correlated theory, such as CCSD­(T),
is arduous due to the high computational cost involved. The present
study reports the possibility of efficiently constructing such a PES
of molecules containing up to 15 atoms and 550 basis functions by
employing the fragment-based molecular tailoring approach (MTA) on
off-the-shelf hardware. The MTA energies at the CCSD­(T)/aug-cc-pVTZ
level for several geometries of three test molecules, viz., acetylacetone, N-methylacetamide, and tropolone, are reported. These energies
are in excellent agreement with their full calculation counterparts
with a time advantage factor of 3–5. The energy barrier from
the ground to transition state is also accurately captured. Further,
we demonstrate the accuracy and efficiency of MTA for estimating the
energy gradients at the CCSD­(T) level. As a further application of
our MTA methodology, the energies of acetylacetone at ∼430
geometries are computed at the CCSD­(T)/aug-cc-pVTZ level and used
for generating a Δ-machine learning (Δ-ML) PES. This leads
to the H-transfer barrier of 3.02 kcal/mol, well in agreement with
the benchmarked barrier of 3.19 kcal/mol. The fidelity of this Δ-ML
PES is examined by geometry optimization and normal mode frequency
calculations of global minima and saddle point geometries. We trust
that the present work is a major development for the rapid and accurate
construction of PES at the CCSD­(T) level for molecules containing
up to 20 atoms and 600 basis functions using off-the-shelf hardware.