Title: On the geometric dependence of the molecular dipole polarizability in water: A benchmark study of higher-order electron correlation, basis set incompleteness error, core electron effects, and zero-point vibrational contributions

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5051458 · OSTI ID:1543885
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Cornell Univ., Ithaca, NY (United States). Baker Lab., Dept. of Chemistry and Chemical Biology
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In this work, we investigate how geometric changes influence the static dipole polarizability ($$α$$) of a water molecule by explicitly computing the corresponding dipole polarizability surface (DPS) across 3125 total (1625 symmetry-unique) geometries using linear response coupled cluster theory including single, double, and triple excitations (LR-CCSDT) and the doubly augmented triple-$$ζ$$ basis set (d-aug-cc-pVTZ). Analytical formulae based on power series expansions of this $ab initio$ surface are generated using linear least-squares analysis and provide highly accurate estimates of this quantity as a function of molecular geometry (i.e., bond and angle variations) in a computationally tractable manner. An additional database, which consists of 25 representative molecular geometries and incorporates a more thorough treatment of both basis sets and core electron effects, is provided as a current benchmark for this quantity and the corresponding leading-order $$C_6$$ dispersion coefficient. This database has been utilized to assess the importance of these effects as well as the relative accuracy that can be obtained using several quantum chemical methods and a library of density functional approximations. In addition to high-level electron correlation methods (like CCSD) and our analytical least-squares formulae, we find that the SCAN0, PBE0, MN15, and B97-2 hybrid functionals yield the most accurate descriptions of the molecular polarizability tensor in H2O. Using first-order perturbation theory, we compute the zero-point vibrational correction to $$α$$ at the CCSDT/d-aug-cc-pVTZ level and find that this correction contributes approximately 3% to the isotropic ($$α$$iso) and nearly 50% to the anisotropic ($$α$$aniso) polarizability values. In doing so, we find that $$α$$iso = 9.8307 bohr3, which is in excellent agreement with the experimental value of 9.83 ± 0.02 bohr3 provided by Russell and Spackman. The DPS reported herein provides a benchmark-quality quantum mechanical estimate of this fundamental quantity of interest and should find extensive use in the development (and assessment) of next-generation force fields and machine-learning based approaches for modeling water in complex condensed-phase environments.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543885
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 149; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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