The multi-configuration self-consistent field method within a polarizable embedded framework

Hedegård, Erik D.; List, Nanna Holmgaard; Jensen, Hans Jørgen Aa.; Kongsted, Jacob

doi:10.1063/1.4811835

Cited by 49 publications

(77 citation statements)

References 83 publications

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“…The implementation described in Ref. [3] gives access to excited states through a state-specific complete active space SCF (CASSCF) or restricted active space SCF (RASSCF) method. As an alternative, excitation energies and oscillator strengths are available through the PE-MCSCF linear response method, which is also described in Ref.…”

Section: Mcscf and Pementioning

confidence: 99%

“…These equations have recently been derived in detail in Refs. [3,15]. Also a few target systems where one would expect that the PE-MCSCF method is to be Erik Donovan Hedegå rd graduated in 2005 from the University of Copenhagen and is currently pursuing a PhD in Kongsteds group at the University of Southern Denmark, and as a visiting researcher at Paul Sabatier University (Toulouse, France) and Lund University (Lund, Sweden).…”

Section: Introductionmentioning

confidence: 99%

“…This perspective is in particular concerned with a recent coupling of the PE method with a multiconfiguration self-consistent field (MCSCF) wave function, including linear response properties. [3] The method is denoted PE-MCSCF and has recently been implemented in a development version of the DALTON program. [4] Direct comparison of experimental and theoretical spectroscopic constants may be very important when interpreting ambiguous experimental data.…”

Section: Introductionmentioning

confidence: 99%

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Polarizable embedding based on multiconfigurational methods: Current developments and the road ahead

Hedegård

Jensen

Kongsted

2014

Int J of Quantum Chemistry

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This perspective gives a brief overview of recent developments within the polarizable embedding (PE) method -a multiscale approach developed over the last years. In particular, we are concerned with a recent coupling of the PE method to a multiconfiguration self-consistent field (MCSCF) code. Current applications and target systems are outlined, and methods to incorporate dynamical correlation are discussed. With respect to dynamical correlation, the focus is on perturbative treatments as well as a range-separated multiconfigurational hybrid between MCSCF and density functional theory (MC-srDFT). A short discussion of CAS active spaces is also given. A few sample results using a retinal chromophore surrounded by a protein environment illustrate both the importance of the choice of active space and the importance of dynamical correlation.

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Section: Mcscf and Pementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Polarizable embedding based on multiconfigurational methods: Current developments and the road ahead

Hedegård

Jensen

Kongsted

2014

Int J of Quantum Chemistry

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“…V pq,s are the electrostatic potential integrals for center s defined through a multipole expansion [30,34,35]…”

Section: Polarizable Embeddingmentioning

confidence: 99%

“…Polarizable Embedding [29][30][31][32][33][34][35][36][37] (PE) relies on a different strategy, namely on atomcentered polarizabilities to represents the fragments in the environment. Contrary to other methods of this kind [38][39][40][41][42][43], PE employs both high-order multipoles and polarizabilities obtained from QM calculations, which makes the PE potential easily customized to a specific environment.…”

Section: Introductionmentioning

confidence: 99%

Polarizable Embedding Density Matrix Renormalization Group

Hedegård

Reiher

2016

J. Chem. Theory Comput.

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The polarizable embedding (PE) approach is a flexible embedding model where a pre-selected region out of a larger system is described quantum mechanically while the interaction with the surrounding environment is modeled through an effective operator. This effective operator represents the environment by atom-centered multipoles and polarizabilities derived from quantum mechanical calculations on (fragments of) the environment. Thereby, the polarization of the environment is explicitly accounted for. Here, we present the coupling of the PE approach with the density matrix renormalization group (DMRG).This PE-DMRG method is particularly suitable for embedded subsystems that feature a dense manifold of frontier orbitals which requires large active spaces.Recovering such static electron-correlation effects in multiconfigurational electronic structure problems, while accounting for both electrostatics and polarization of a surrounding environment, allows us to describe strongly correlated electronic structures in complex molecular environments. We investigate various embedding potentials for the well-studied first excited state of water with active spaces that correspond to a full configuration-interaction treatment.

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Optimization and transferability of non‐electrostatic repulsion in the polarizable density embedding model

2017

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Embedding techniques in combination with response theory represent a successful approach to calculate molecular properties and excited states in large molecular systems such as solutions and proteins. Recently, the polarizable embedding model has been extended by introducing explicit electronic densities of the molecules in the nearest environment, resulting in the polarizable density embedding (PDE) model. This improvement provides a better description of the intermolecular interactions at short distances. However, the electronic densities of the environment molecules are calculated in isolation, which results in overestimation of the non-electrostatic repulsion, thereby requiring a scaling of this term. In this work, an optimal scaling factor for the non-electrostatic repulsion term is examined by comparing intermolecular interaction energies obtained with embedding techniques to reference interaction energies calculated on the basis of full quantum-mechanical calculations. The obtained optimal factors are used in PDE calculations of various ground- and excited-state properties of molecules embedded in solvents described as polarizable environments. © 2017 Wiley Periodicals, Inc.

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The multi-configuration self-consistent field method within a polarizable embedded framework

Cited by 49 publications

References 83 publications

Polarizable embedding based on multiconfigurational methods: Current developments and the road ahead

Polarizable embedding based on multiconfigurational methods: Current developments and the road ahead

Polarizable Embedding Density Matrix Renormalization Group

Optimization and transferability of non‐electrostatic repulsion in the polarizable density embedding model

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