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Analytical gradients for projection-based wavefunction-in-DFT embedding

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Analytical gradients for projection-based wavefunction-in-DFT embedding. / Lee, Sebastian; Ding, Feizhi; Manby, Fred; Miller, Thomas.

In: Journal of Chemical Physics, Vol. 151, 064112 (2019), 09.08.2019.

Research output: Contribution to journalArticle

Harvard

Lee, S, Ding, F, Manby, F & Miller, T 2019, 'Analytical gradients for projection-based wavefunction-in-DFT embedding', Journal of Chemical Physics, vol. 151, 064112 (2019). https://doi.org/10.1063/1.5109882

APA

Lee, S., Ding, F., Manby, F., & Miller, T. (2019). Analytical gradients for projection-based wavefunction-in-DFT embedding. Journal of Chemical Physics, 151, [064112 (2019)]. https://doi.org/10.1063/1.5109882

Vancouver

Lee S, Ding F, Manby F, Miller T. Analytical gradients for projection-based wavefunction-in-DFT embedding. Journal of Chemical Physics. 2019 Aug 9;151. 064112 (2019). https://doi.org/10.1063/1.5109882

Author

Lee, Sebastian ; Ding, Feizhi ; Manby, Fred ; Miller, Thomas. / Analytical gradients for projection-based wavefunction-in-DFT embedding. In: Journal of Chemical Physics. 2019 ; Vol. 151.

Bibtex

@article{35bce610e8f2467f9288b24acd0d8ab0,
title = "Analytical gradients for projection-based wavefunction-in-DFT embedding",
abstract = "Projection-based embedding provides a simple, robust, and accurate approach for describing a small part of a chemical system at the level of a correlated wavefunction (WF) method, while the remainder of the system is described at the level of density functional theory (DFT). Here, we present the derivation, implementation, and numerical demonstration of analytical nuclear gradients for projection-based wavefunction-in-density functional theory (WF-in-DFT) embedding. The gradients are formulated in the Lagrangian framework to enforce orthogonality, localization, and Brillouin constraints on the molecular orbitals. An important aspect of the gradient theory is that WF contributions to the total WF-in-DFT gradient can be simply evaluated using existing WF gradient implementations without modification. Another simplifying aspect is that Kohn-Sham (KS) DFT contributions to the projection-based embedding gradient do not require knowledge of the WF calculation beyond the relaxed WF density. Projection-based WF-in-DFT embedding gradients are thus easily generalized to any combination of WF and KS-DFT methods. We provide a numerical demonstration of the method for several applications, including a calculation of a minimum energy pathway for a hydride transfer in a cobalt-based molecular catalyst using the nudged-elastic-band method at the coupled-cluster single double-in-DFT level of theory, which reveals large differences from the transition state geometry predicted using DFT.I. INTRODUCTION",
author = "Sebastian Lee and Feizhi Ding and Fred Manby and Thomas Miller",
year = "2019",
month = "8",
day = "9",
doi = "10.1063/1.5109882",
language = "English",
volume = "151",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics (AIP)",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Analytical gradients for projection-based wavefunction-in-DFT embedding

AU - Lee, Sebastian

AU - Ding, Feizhi

AU - Manby, Fred

AU - Miller, Thomas

PY - 2019/8/9

Y1 - 2019/8/9

N2 - Projection-based embedding provides a simple, robust, and accurate approach for describing a small part of a chemical system at the level of a correlated wavefunction (WF) method, while the remainder of the system is described at the level of density functional theory (DFT). Here, we present the derivation, implementation, and numerical demonstration of analytical nuclear gradients for projection-based wavefunction-in-density functional theory (WF-in-DFT) embedding. The gradients are formulated in the Lagrangian framework to enforce orthogonality, localization, and Brillouin constraints on the molecular orbitals. An important aspect of the gradient theory is that WF contributions to the total WF-in-DFT gradient can be simply evaluated using existing WF gradient implementations without modification. Another simplifying aspect is that Kohn-Sham (KS) DFT contributions to the projection-based embedding gradient do not require knowledge of the WF calculation beyond the relaxed WF density. Projection-based WF-in-DFT embedding gradients are thus easily generalized to any combination of WF and KS-DFT methods. We provide a numerical demonstration of the method for several applications, including a calculation of a minimum energy pathway for a hydride transfer in a cobalt-based molecular catalyst using the nudged-elastic-band method at the coupled-cluster single double-in-DFT level of theory, which reveals large differences from the transition state geometry predicted using DFT.I. INTRODUCTION

AB - Projection-based embedding provides a simple, robust, and accurate approach for describing a small part of a chemical system at the level of a correlated wavefunction (WF) method, while the remainder of the system is described at the level of density functional theory (DFT). Here, we present the derivation, implementation, and numerical demonstration of analytical nuclear gradients for projection-based wavefunction-in-density functional theory (WF-in-DFT) embedding. The gradients are formulated in the Lagrangian framework to enforce orthogonality, localization, and Brillouin constraints on the molecular orbitals. An important aspect of the gradient theory is that WF contributions to the total WF-in-DFT gradient can be simply evaluated using existing WF gradient implementations without modification. Another simplifying aspect is that Kohn-Sham (KS) DFT contributions to the projection-based embedding gradient do not require knowledge of the WF calculation beyond the relaxed WF density. Projection-based WF-in-DFT embedding gradients are thus easily generalized to any combination of WF and KS-DFT methods. We provide a numerical demonstration of the method for several applications, including a calculation of a minimum energy pathway for a hydride transfer in a cobalt-based molecular catalyst using the nudged-elastic-band method at the coupled-cluster single double-in-DFT level of theory, which reveals large differences from the transition state geometry predicted using DFT.I. INTRODUCTION

U2 - 10.1063/1.5109882

DO - 10.1063/1.5109882

M3 - Article

VL - 151

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

M1 - 064112 (2019)

ER -