Decomposed Mean-Field Simulations of Local Properties in Condensed Phases.

  title={Decomposed Mean-Field Simulations of Local Properties in Condensed Phases.},
  author={Janus Juul Eriksen},
  journal={The journal of physical chemistry letters},
  • J. J. Eriksen
  • Published 26 April 2021
  • Chemistry
  • The journal of physical chemistry letters
The present work demonstrates a robust protocol for probing localized electronic structure in condensed-phase systems, operating in terms of a recently proposed theory for decomposing the results of Kohn-Sham density functional theory in a basis of spatially localized molecular orbitals. In an initial application to liquid, ambient water and the assessment of the solvation energy and the embedded dipole moment of H2O in solution, we find that both properties are amplified on average-in… 
3 Citations

Figures from this paper

Decomposing Chemical Space: Applications to the Machine Learning of Atomic Energies.

We apply a number of atomic decomposition schemes across the standard QM7 data set─a small model set of organic molecules at equilibrium geometry─to inspect the possible emergence of trends among

Electronic excitations through the prism of mean-field decomposition techniques.

The potential of mean-field decomposition techniques in interpreting electronic transitions in molecules is explored, in particular, the usefulness of these for offering computational signatures of

Mean-field density matrix decompositions.

How decomposed mean-field theory makes it possible to expose and amplify compositional features in the context of machine-learned quantum chemistry is demonstrated by improving upon the granularity of the underlying data.

Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments.

Self-attractive Hartree (SAH) decomposition is presented to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally.

A general purpose model for the condensed phases of water: TIP4P/2005.

A potential model intended to be a general purpose model for the condensed phases of water is presented, which gives excellent predictions for the densities at 1 bar with a maximum density at 278 K and an averaged difference with experiment of 7 x 10(-4) g/cm3.

How many water molecules are needed to solvate one?

It is found that double-acceptor double-donor tetrahedral coordination constituting the standard picture is necessary but not sufficient, and that particular care must be reserved for the quantum description of the combination band due to the coupling of the central monomer bending mode with network librations.

Density-functional thermochemistry. III. The role of exact exchange

Despite the remarkable thermochemical accuracy of Kohn–Sham density‐functional theories with gradient corrections for exchange‐correlation [see, for example, A. D. Becke, J. Chem. Phys. 96, 2155

Comparison of simple potential functions for simulating liquid water

Classical Monte Carlo simulations have been carried out for liquid water in the NPT ensemble at 25 °C and 1 atm using six of the simpler intermolecular potential functions for the water dimer:

How good are polarizable and flexible models for water: Insights from a many-body perspective.

It is found that, while correctly reproducing the energetics of minimum-energy structures, the polarizable models examined in this study suffer from inadequate representations of many-body effects for distorted configurations.

A fast intrinsic localization procedure applicable for ab initio and semiempirical linear combination of atomic orbital wave functions

A new intrinsic localization algorithm is suggested based on a recently developed mathematical measure of localization. No external criteria are used to define a priori bonds, lone pairs, and core

Jacob’s ladder of density functional approximations for the exchange-correlation energy

The ground-state energy and density of a many-electron system are often calculated by Kohn-Sham density functional theory. We describe a ladder of approximations for the exchange-correlation energy