Excited States in Solution through Polarizable Embedding

Olsen, Jógvan Magnus Haugaard; Aidas, Kęstutis; Kongsted, Jacob

doi:10.1021/ct1003803

Cited by 321 publications

(614 citation statements)

References 64 publications

(158 reference statements)

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“…It has previously been demonstrated that the RMSD from QM ESPs decreases almost as sharply for ESP-fitted charges as for a charge distribution with multipoles up to quadrupoles or octopoles. 5,17,19 The observation that the error in the ESP decreases sharply with the distance at which it is evaluated will be taken advantage of in the next section.…”

Section: Molecular Electrostatic Potentials Of the Solvent Moleculesmentioning

confidence: 99%

Averaged Solvent Embedding Potential Parameters for Multiscale Modeling of Molecular Properties

Beerepoot

Steindal

List

et al. 2016

J. Chem. Theory Comput.

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We derive and validate averaged solvent parameters for embedding potentials to be used in polarizable embedding quantum mechanics/molecular mechanics (QM/MM) molecular property calculations of solutes in organic solvents. The parameters are solvent-specific atom-centered partial charges and isotropic polarizabilities averaged over a large number of geometries of solvent molecules. The use of averaged parameters 1 reduces the computational cost to obtain the embedding potential, which can otherwise be a rate-limiting step in calculations involving large environments. The parameters are evaluated by analyzing the quality of the resulting molecular electrostatic potentials with respect to full QM potentials. We show that a combination of geometry-specific parameters for solvent molecules close to the QM region and averaged parameters for solvent molecules further away allows for efficient polarizable embedding multiscale modeling without compromising the accuracy. The results are promising for the development of general embedding parameters for biomolecules, where the reduction in computational cost can be considerable.

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Section: Molecular Electrostatic Potentials Of the Solvent Moleculesmentioning

confidence: 99%

Averaged Solvent Embedding Potential Parameters for Multiscale Modeling of Molecular Properties

Beerepoot

Steindal

List

et al. 2016

J. Chem. Theory Comput.

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“…This article focuses on the perspectives of recent developments within the polarizable embedding (PE) method, [1] which is a multiscale approach developed over the last years. Similar methods, such as the effective fragment potential method, [2] have focused mainly on relative energies and molecular geometries, whereas the PE method has its primary focus on molecular response properties as well as spectroscopic constants.…”

Section: Introductionmentioning

confidence: 99%

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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“…The importance of diffuse functions in the first excitation of the water molecule was previously highlighted [101]. We chose a 6-31++G* basis set [118][119][120], meaning that DMRG (10,30)[512] corresponds to the active space of a full configuration interaction (FCI) calculation. However, although this small basis set will not yield accurate results, it is a suitable choice here as it permits us to carry out a FCI-type DMRG calculation that does not require further consideration of dynamical correlation effects.…”

Section: Computational Methodsologymentioning

confidence: 99%

“…The PE scheme [29,30] divides the environment into (molecular) fragments. We associate to each of these fragments a set of electrostatic multipoles, usually localized at the atomic centers [85].…”

Section: Polarizable Embeddingmentioning

confidence: 99%

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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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Excited States in Solution through Polarizable Embedding

Cited by 321 publications

References 64 publications

Averaged Solvent Embedding Potential Parameters for Multiscale Modeling of Molecular Properties

Averaged Solvent Embedding Potential Parameters for Multiscale Modeling of Molecular Properties

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

Polarizable Embedding Density Matrix Renormalization Group

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