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Title: Gaussian Basis Set and Planewave Relativistic Spin-Orbit Methods in NWChem

Abstract

Relativistic spin-orbit density functional theory (DFT) methods have been implemented in the molecular Gaussian DFT and pseudopotential plane-wave DFT modules of the NWChem electronic-structure program. The Gaussian basis set implementation is based upon the zeroth-order regular approximation (ZORA) while the planewave implementation uses spin-orbit pseudopotentials that are directly generated from the atomic Dirac-Kohn-Sham wavefunctions or atomic ZORA-Kohn-Sham wavefunctions. Compared to solving the full Dirac equation these methods are computationally efficient, but robust enough for a realistic description of relativistic effects such as spin-orbit splitting, molecular orbital hybridization, and core effects. Both methods have been applied to a variety of small molecules, including I$$_{\text{2}}$$, IF, HI, Br$$_{\text{2}}$$, Bi$$_{\text{2}}$$, AuH, and Au$$_{\text{2}}$$, using various exchange-correlation functionals. Our results are in good agreement with experiment and previously reported calculations.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
951835
Report Number(s):
PNNL-SA-61552
29990; KC0302030; TRN: US200913%%71
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Theory and Computation, 5(3):491-499
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY FUNCTIONAL METHOD; L-S COUPLING; APPROXIMATIONS; DIRAC EQUATION; ELECTRONIC STRUCTURE; IODINE; BROMINE; BISMUTH; GOLD HYDRIDES; GOLD; HALIDES; NWChem; Relativistic Density Functional Theory; Environmental Molecular Sciences Laboratory

Citation Formats

Nichols, Patrick J, Govind, Niranjan, Bylaska, Eric J, and De Jong, Wibe A. Gaussian Basis Set and Planewave Relativistic Spin-Orbit Methods in NWChem. United States: N. p., 2009. Web. doi:10.1021/ct8002892.
Nichols, Patrick J, Govind, Niranjan, Bylaska, Eric J, & De Jong, Wibe A. Gaussian Basis Set and Planewave Relativistic Spin-Orbit Methods in NWChem. United States. https://doi.org/10.1021/ct8002892
Nichols, Patrick J, Govind, Niranjan, Bylaska, Eric J, and De Jong, Wibe A. Wed . "Gaussian Basis Set and Planewave Relativistic Spin-Orbit Methods in NWChem". United States. https://doi.org/10.1021/ct8002892.
@article{osti_951835,
title = {Gaussian Basis Set and Planewave Relativistic Spin-Orbit Methods in NWChem},
author = {Nichols, Patrick J and Govind, Niranjan and Bylaska, Eric J and De Jong, Wibe A},
abstractNote = {Relativistic spin-orbit density functional theory (DFT) methods have been implemented in the molecular Gaussian DFT and pseudopotential plane-wave DFT modules of the NWChem electronic-structure program. The Gaussian basis set implementation is based upon the zeroth-order regular approximation (ZORA) while the planewave implementation uses spin-orbit pseudopotentials that are directly generated from the atomic Dirac-Kohn-Sham wavefunctions or atomic ZORA-Kohn-Sham wavefunctions. Compared to solving the full Dirac equation these methods are computationally efficient, but robust enough for a realistic description of relativistic effects such as spin-orbit splitting, molecular orbital hybridization, and core effects. Both methods have been applied to a variety of small molecules, including I$_{\text{2}}$, IF, HI, Br$_{\text{2}}$, Bi$_{\text{2}}$, AuH, and Au$_{\text{2}}$, using various exchange-correlation functionals. Our results are in good agreement with experiment and previously reported calculations.},
doi = {10.1021/ct8002892},
url = {https://www.osti.gov/biblio/951835}, journal = {Journal of Chemical Theory and Computation, 5(3):491-499},
number = 3,
volume = 5,
place = {United States},
year = {2009},
month = {1}
}