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Title: Multipole Expansion of Atomic Electron Density Fluctuation Interactions in the Density-Functional Tight-Binding Method

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]
  1. Boston Univ., MA (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Univ. of Bremen (Germany)
  3. Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
  4. Boston Univ., MA (United States)
  5. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations

The accuracy of the density-functional tight-binding (DFTB) method in describing noncovalent interactions is limited due to its reliance on monopole-based spherical charge densities. In this study, we present a multipole-extended second-order DFTB (mDFTB2) method that takes into account atomic dipole and quadrupole interactions. Furthermore, we combine the multipole expansion with the monopole-based third-order contribution, resulting in the mDFTB3 method. To assess the accuracy of mDFTB2 and mDFTB3, we evaluate their performance in describing noncovalent interactions, proton transfer barriers, and dipole moments. Here, our benchmark results show promising improvements even when using the existing electronic parameters optimized for the original DFTB3 model. Both mDFTB2 and mDFTB3 outperform their monopole-based counterparts, DFTB2 and DFTB3, in terms of accuracy. While mDFTB2 and mDFTB3 perform comparably for neutral and positively charged systems, mDFTB3 exhibits superior performance over mDFTB2 when dealing with negatively charged systems and proton transfers. Overall, the incorporation of the multipole expansion significantly enhances the accuracy of the DFTB method in describing noncovalent interactions and proton transfers.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
2251622
Alternate ID(s):
OSTI ID: 2290324
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 21 Vol. 19; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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molecular structure
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