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

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 126; no. 8; pp. 1458 - 1464
• Main Authors: Khire, Subodh S, Gurav, Nalini D, Nandi, Apurba, Gadre, Shridhar R
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.03.2022
• Subjects: A: New Tools and Methods in Experiment and Theory
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.2c00025

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.