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Multicomponent density functional theory study of the interplay between electron-electron and electron-proton
Andrew Sirjoosingh1, Michael V Pak, Sharon Hammes-Schiffer
1Department of Chemistry, 104 Chemistry Building, Pennsylvania State University, University Park, Pennsylvania 16802, USA.
The Journal of Chemical Physics
|May 16, 2012
Summary
This study introduces a new electron-proton correlation functional within nuclear-electronic orbital density functional theory (NEO-DFT). The new functional accounts for kinetic energy contributions, improving accuracy for quantum mechanical proton treatments.
Area of Science:
- Quantum Chemistry
- Computational Physics
- Materials Science
Background:
- Nuclear-electronic orbital density functional theory (NEO-DFT) treats electrons and protons quantum mechanically.
- Existing electron-proton correlation functionals neglected kinetic energy contributions.
- Accurate correlation functionals are crucial for quantum chemical calculations.
Purpose of the Study:
- To derive and assess a new electron-proton correlation functional including kinetic energy contributions within NEO-DFT.
- To evaluate the performance of NEO-DFT with different correlation functionals.
- To understand the interplay between electron-electron and electron-proton correlation.
Main Methods:
- Derivation of a new electron-proton correlation functional using the adiabatic connection formula in multicomponent DFT.
- Application of the nuclear-electronic orbital density functional theory (NEO-DFT) approach.
- Assessment of the functional's performance with established electronic exchange-correlation functionals.
Main Results:
- The newly derived electron-proton correlation functional captures increased hydrogen vibrational stretching frequencies.
- Electron-proton and electron-electron correlation effects were found to be largely independent and additive.
- The developed functionals can be combined without re-parameterization.
Conclusions:
- The inclusion of kinetic energy in electron-proton correlation functionals improves NEO-DFT accuracy.
- Electron-proton and electron-electron correlation can be treated separately in these model systems.
- This work facilitates the independent development and combination of correlation functionals.
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