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A new framework for frequency-dependent polarizable force fields
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DOI：10.1063/5.0115151.png)
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Abstract
En 中文
A frequency-dependent extension of the polarizable force field Atom-Condensed Kohn-Sham density functional theory approximated to the second-order (ACKS2) [Verstraelen et al., J. Chem. Phys. 141, 194114 (2014)] is proposed, referred to as ACKS2 omega. The method enables theoretical predictions of dynamical response properties of finite systems after partitioning of the frequency-dependent molecular response function. Parameters in this model are computed simply as expectation values of an electronic wavefunction, and the hardness matrix is entirely reused from ACKS2 as an adiabatic approximation is used. A numerical validation shows that accurate models can already be obtained with atomic monopoles and dipoles. Absorption spectra of 42 organic and inorganic molecular monomers are evaluated using ACKS2 omega, and our results agree well with the time-dependent DFT calculations. Also for the calculation of C-6 dispersion coefficients, ACKS2 omega closely reproduces its TDDFT reference. When parameters for ACKS2 omega are derived from a PBE/aug-cc-pVDZ ground state, it reproduces experimental values for 903 organic and inorganic intermolecular pairs with an MAPE of 3.84%. Our results confirm that ACKS2 omega offers a solid connection between the quantum-mechanical description of frequency-dependent response and computationally efficient force-field models. Published under an exclusive license by AIP Publishing.
Keywords:
DENSITY-FUNCTIONAL THEORY
ELECTRONEGATIVITY EQUALIZATION METHOD
MOLECULAR-DYNAMICS SIMULATIONS
FLUCTUATING CHARGE
FLOQUET FORMULATION
LINEAR-RESPONSE
EXCITATION-ENERGIES
ATOMIC CHARGES
MODEL
WATER