Embedding Fragment ab Initio Model Potentials in CASSCF/CASPT2 Calculations of Doped Solids: Implementation and Applications

Swerts, Ben; Chibotaru, Liviu F.; Lindh, Roland; Seijo, Luis; Barandiarán, Zoila; Clima, Sergiu; Pierloot, Kristine; Hendrickx, Marc

doi:10.1021/ct7003148

Cited by 55 publications

(46 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the limit of μ → ∞, the MOs of subsystem A are constrained to be mutually orthogonal with those of subsystem B. [36][37][38][39][40][41][42][43] Enforcement of this orthogonality condition eliminates the need for an OEP calculation, since non-additive contributions to the kinetic energy vanish in this limit. The embedded SCF calculation using the Fock matrix in Eq.…”

Section: Projection-based Embeddingmentioning

confidence: 99%

Accurate basis set truncation for wavefunction embedding

Barnes

Goodpaster

Manby³

et al. 2013

The Journal of Chemical Physics

127

View full text Add to dashboard Cite

Density functional theory (DFT) provides a formally exact framework for performing embedded subsystem electronic structure calculations, including DFT-in-DFT and wavefunction theory-in-DFT descriptions. In the interest of efficiency, it is desirable to truncate the atomic orbital basis set in which the subsystem calculation is performed, thus avoiding high-order scaling with respect to the size of the MO virtual space. In this study, we extend a recently introduced projection-based embedding method [F. R. Manby, M. Stella, J. D. Goodpaster, and T. F. Miller III, J. Chem. Theory Comput. 8, 2564 (2012)] to allow for the systematic and accurate truncation of the embedded subsystem basis set. The approach is applied to both covalently and non-covalently bound test cases, including water clusters and polypeptide chains, and it is demonstrated that errors associated with basis set truncation are controllable to well within chemical accuracy. Furthermore, we show that this approach allows for switching between accurate projection-based embedding and DFT embedding with approximate kinetic energy (KE) functionals; in this sense, the approach provides a means of systematically improving upon the use of approximate KE functionals in DFT embedding. © 2013 AIP Publishing LLC. [http://dx

show abstract

Section: Projection-based Embeddingmentioning

confidence: 99%

Accurate basis set truncation for wavefunction embedding

Barnes

Goodpaster

Manby³

et al. 2013

The Journal of Chemical Physics

127

View full text Add to dashboard Cite

show abstract

“…A variety of other schemes have been proposed and applied in the past for this purpose, and some of them were already discussed above. As particular examples, we mention continuum solvation models [315][316][317][318][319][320][321], effective potential methods [332,333], including the so-called ab initio model potentials, which are directly based on the electron densities of the environment [334,335], QM/MM schemes [142,[154][155][156][157][158], or general multi-layer approaches such as the ONIOM model [159,160].…”

Section: Environmental Effects On Molecular Properties and Valence Exmentioning

confidence: 99%

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

2010

View full text Add to dashboard Cite

“…(An extension of the embedding AIMP method for multiatomic ions has been recently implemented, 19 but it will not be used in this work.) It starts with the assumption of an ionic limit for the host and with the identification of its ions; in the sample case these are Ce …”

Section: B Self-consistent Embedded Ionsmentioning

confidence: 99%

Improved Embedding Ab Initio Model Potentials for Embedded Cluster Calculations

et al. 2009

Self Cite

View full text Add to dashboard Cite

An improvement in the method of production of embedding ab initio model potentials (AIMP) for embedded cluster calculations in ionic solids is proposed and applied to the oxides CeAlO 3 , CeO 2 , and UO 2 . The improvement affects the calculation of one of the AIMP components, the Pauli repulsion operator, which prevents the cluster electrons from collapsing onto the occupied orbitals of the host in embedded cluster calculations and, so, their over occupancy. The linear constants involved in such operator are proposed to be obtained in embedded cluster calculations in the perfect host, with the requirement that local structures calculated with working embedded clusters of relatively small size agree with those calculated with reference embedded clusters of much larger size.

show abstract

Embedding Fragment ab Initio Model Potentials in CASSCF/CASPT2 Calculations of Doped Solids: Implementation and Applications

Cited by 55 publications

References 43 publications

Accurate basis set truncation for wavefunction embedding

Accurate basis set truncation for wavefunction embedding

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

Improved Embedding Ab Initio Model Potentials for Embedded Cluster Calculations

Contact Info

Product

Resources

About