Enabling Rapid and Accurate Construction of CCSD(T)-Level Potential Energy Surface of Large Molecules Using Molecular Tailoring Approach.
| Title: | Enabling Rapid and Accurate Construction of CCSD(T)-Level Potential Energy Surface of Large Molecules Using Molecular Tailoring Approach. |
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| Authors: | Khire SS; Department of Scientific Computing, Modelling and Simulation, Savitribai Phule Pune University, Pune 411 007, India.; Gurav ND; Department of Scientific Computing, Modelling and Simulation, Savitribai Phule Pune University, Pune 411 007, India.; Nandi A; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, United States.; Gadre SR; Department of Scientific Computing, Modelling and Simulation, Savitribai Phule Pune University, Pune 411 007, India. |
| Source: | The journal of physical chemistry. A [J Phys Chem A] 2022 Mar 03; Vol. 126 (8), pp. 1458-1464. Date of Electronic Publication: 2022 Feb 16. |
| Publication Type: | Journal Article |
| Language: | English |
| Journal Info: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 9890903 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5215 (Electronic) Linking ISSN: 10895639 NLM ISO Abbreviation: J Phys Chem A Subsets: MEDLINE; PubMed not MEDLINE |
| Imprint Name(s): | Original Publication: Washington, D.C. : American Chemical Society, c1997- |
| Abstract: | 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. |
| Entry Date(s): | Date Created: 20220216 Latest Revision: 20220303 |
| Update Code: | 20260130 |
| DOI: | 10.1021/acs.jpca.2c00025 |
| PMID: | 35170973 |
| Database: | MEDLINE |
Journal Article