TY - JOUR
T1 - Potential Functional Embedding Theory at the Correlated Wave Function Level. 2. Error Sources and Performance Tests
AU - Cheng, Jin
AU - Yu, Kuang
AU - Libisch, Florian
AU - Dieterich, Johannes M.
AU - Carter, Emily A.
N1 - Funding Information:
We are grateful to the National Science Foundation (Award No. 1265700) and the Department of Energy, Office of Science, Basic Energy Sciences (Award No. DE-SC0002120) for support of this work. The authors are pleased to acknowledge computational support from the TIGRESS high performance computer center at Princeton University which is jointly administered by the Princeton Institute for Computational Science and Engineering and the Princeton University Office of Information Technology. We also thank Nari Baughman for her help in editing the paper.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/14
Y1 - 2017/3/14
N2 - Quantum mechanical embedding theories partition a complex system into multiple spatial regions that can use different electronic structure methods within each, to optimize trade-offs between accuracy and cost. The present work incorporates accurate but expensive correlated wave function (CW) methods for a subsystem containing the phenomenon or feature of greatest interest, while self-consistently capturing quantum effects of the surroundings using fast but less accurate density functional theory (DFT) approximations. We recently proposed two embedding methods [for a review, see: Acc. Chem. Res. 2014, 47, 2768 ]: density functional embedding theory (DFET) and potential functional embedding theory (PFET). DFET provides a fast but non-self-consistent density-based embedding scheme, whereas PFET offers a more rigorous theoretical framework to perform fully self-consistent, variational CW/DFT calculations [as defined in part 1, CW/DFT means subsystem 1(2) is treated with CW(DFT) methods]. When originally presented, PFET was only tested at the DFT/DFT level of theory as a proof of principle within a planewave (PW) basis. Part 1 of this two-part series demonstrated that PFET can be made to work well with mixed Gaussian type orbital (GTO)/PW bases, as long as optimized GTO bases and consistent electron-ion potentials are employed throughout. Here in part 2 we conduct the first PFET calculations at the CW/DFT level and compare them to DFET and full CW benchmarks. We test the performance of PFET at the CW/DFT level for a variety of types of interactions (hydrogen bonding, metallic, and ionic). By introducing an intermediate CW/DFT embedding scheme denoted DFET/PFET, we show how PFET remedies different types of errors in DFET, serving as a more robust type of embedding theory.
AB - Quantum mechanical embedding theories partition a complex system into multiple spatial regions that can use different electronic structure methods within each, to optimize trade-offs between accuracy and cost. The present work incorporates accurate but expensive correlated wave function (CW) methods for a subsystem containing the phenomenon or feature of greatest interest, while self-consistently capturing quantum effects of the surroundings using fast but less accurate density functional theory (DFT) approximations. We recently proposed two embedding methods [for a review, see: Acc. Chem. Res. 2014, 47, 2768 ]: density functional embedding theory (DFET) and potential functional embedding theory (PFET). DFET provides a fast but non-self-consistent density-based embedding scheme, whereas PFET offers a more rigorous theoretical framework to perform fully self-consistent, variational CW/DFT calculations [as defined in part 1, CW/DFT means subsystem 1(2) is treated with CW(DFT) methods]. When originally presented, PFET was only tested at the DFT/DFT level of theory as a proof of principle within a planewave (PW) basis. Part 1 of this two-part series demonstrated that PFET can be made to work well with mixed Gaussian type orbital (GTO)/PW bases, as long as optimized GTO bases and consistent electron-ion potentials are employed throughout. Here in part 2 we conduct the first PFET calculations at the CW/DFT level and compare them to DFET and full CW benchmarks. We test the performance of PFET at the CW/DFT level for a variety of types of interactions (hydrogen bonding, metallic, and ionic). By introducing an intermediate CW/DFT embedding scheme denoted DFET/PFET, we show how PFET remedies different types of errors in DFET, serving as a more robust type of embedding theory.
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U2 - 10.1021/acs.jctc.6b01011
DO - 10.1021/acs.jctc.6b01011
M3 - Article
C2 - 28125226
AN - SCOPUS:85015234212
SN - 1549-9618
VL - 13
SP - 1081
EP - 1093
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 3
ER -