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Published on: July 19, 2019
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Range Separation of the Interaction Potential in Intermolecular and Intramolecular Symmetry-Adapted Perturbation
Du Luu1, Clemence Corminboeuf2, Konrad Patkowski1
1Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, United States.
Journal of Chemical Theory and Computation
|September 10, 2024
Summary
Range-separated symmetry-adapted perturbation theory (SAPT) offers a new way to analyze molecular interactions. This method accurately approximates noncovalent energies, even capturing short-range effects usually missed by other techniques.
Area of Science:
- Computational chemistry
- Quantum chemistry
- Molecular interactions
Background:
- Symmetry-adapted perturbation theory (SAPT) is widely used for calculating noncovalent interactions.
- Intramolecular SAPT (ISAPT) extends this to interactions within a single molecule.
- Current methods struggle to accurately capture both long-range and short-range interaction effects simultaneously.
Purpose of the Study:
- To explore a novel range-separated approach for SAPT and ISAPT.
- To investigate the effectiveness of Coulomb potential splitting using Gaussian and error functions.
- To assess the accuracy of approximating interaction energies using only long-range contributions.
Main Methods:
- Applied range separation to the Coulomb potential (1/r) into long-range and short-range components.
- Utilized Gaussian and error function splittings for the potential.
- Tested the method on various intermolecular and intramolecular complexes.
- Compared range-separated SAPT/ISAPT results with complete SAPT/ISAPT calculations.
Main Results:
- Range-separated SAPT and ISAPT energy corrections showed reasonable agreement with full SAPT/ISAPT data.
- The long-range interaction potential, when range-separated, provided a useful account of short-range terms.
- This contrasts with the limitations of multipole expansions in capturing charge penetration and exchange effects.
- Optimal consistency was achieved with error-function separation applied to all interaction terms.
Conclusions:
- Range-separated SAPT/ISAPT is a viable alternative for analyzing noncovalent interactions.
- This approach effectively incorporates crucial short-range effects.
- It represents a step towards fragmentation-free decomposition of intramolecular nonbonded energy.
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