Excited states in large molecular systems through polarizable embedding

List, Nanna Holmgaard; Olsen, Jógvan Magnus Haugaard; Kongsted, Jacob

doi:10.1039/c6cp03834d

Cited by 87 publications

(113 citation statements)

References 134 publications

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“…[41][42][43][44][45] When combined with excited state formulations, these methods account for the electronic rearrangement of the solvent in response to the excitation of the solute. [46][47][48][49][50] Fragment-based methods [51,52] bridge the realms of MM and fully QM solvent models, both in terms of accuracy and computational cost.…”

Section: Explicit Solvent Modelsmentioning

confidence: 99%

Modeling absorption spectra of molecules in solution

Zuehlsdorff

Isborn

2018

Int J of Quantum Chemistry

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The presence of solvent tunes many properties of a molecule, such as its ground and excited state geometry, dipole moment, excitation energy, and absorption spectrum. Because the energy of the system will vary depending on the solvent configuration, explicit solute-solvent interactions are key to understanding solution-phase reactivity and spectroscopy, simulating accurate inhomogeneous broadening, and predicting absorption spectra. In this tutorial review, we give an overview of factors to consider when modeling excited states of molecules interacting with explicit solvent. We provide practical guidelines for sampling solute-solvent configurations, choosing a solvent model, performing the excited state electronic structure calculations, and computing spectral lineshapes. We also present our recent results combining the vertical excitation energies computed from an ensemble of solute-solvent configurations with the vibronic spectra obtained from a small number of frozen solvent configurations, resulting in improved simulation of absorption spectra for molecules in solution.excited states, TDDFT, solvation, inhomogeneous broadening, absorption spectra | INTRODUCTIONThe presence of solvent around a molecule affects its energy, properties, dynamics, and reactivity, in both the ground and excited state. Because many excited state phenomena of chemical interest happen in solution and in complex interfacial environments, including photosynthesis, photocatalysis, photoinduced charge and proton transfer, and fluorescence in biological systems, it is important to be able to model these excited state reactions while accurately simulating the solvent environment. In addition, both static and time-resolved absorption and fluorescence spectroscopies serve as useful tools to elucidate chemical reactions and pathways, and simulation of these solution-phase spectra can help to achieve understanding of the electronic rearrangements governing chemical reactions.If theoretical models are to provide reliable simulations of solution-phase chemistry, accurate models of the solvent environment are required.The solvent environment can have a strong influence on an absorption spectrum due to polarization and direct solute-solvent interactions such as hydrogen bonding. Therefore, the modeling of absorption spectra of molecules in solution is often considered a vital step in developing and benchmarking methods to account for the complex solvent environment.Although continuum solvent approaches are computationally attractive because they use the bulk properties of the solvent to polarize a solute, and thus, usually do not sample solute-solvent configurations, in reality it is specific solvent configurations rather than a solvent continuum that determine excited state properties. Also, the simulation of spectral lineshapes, such as those shown in Figure 1 that include both the highenergy tail due to vibronic transitions and the inhomogeneous broadening due to solute-solvent interactions, poses a significant challenge for continuum methods. T...

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Section: Explicit Solvent Modelsmentioning

confidence: 99%

Modeling absorption spectra of molecules in solution

Zuehlsdorff

Isborn

2018

Int J of Quantum Chemistry

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“…(33) and (34) reduce exactly to the form of the so-called dynamic reaction field and the effective external field (EEF) effects, the latter also referred to as the local field effect, appearing in polarizable embedding. 29,47 The effective external field effect is of the same origin as the cavity-field effect in polarizable continuum models leading to effective properties, [62][63][64][65] but is defined with respect to the external probing field rather than the Maxwell field within the dielectric. 66 It should also be noted that the same terms describe the so-called image-and near-field effects in the context of treating molecules adsorbed to metal nanoparticles.…”

Section: [2]mentioning

confidence: 99%

“…Both FDE [21][22][23][24][25] and polarizable embedding approaches [26][27][28][29][30][31][32] have been generalized to a response formalism to allow for the calculation of response and transition properties of molecules embedded in large molecular complexes. The computational cost associated with the explicit coupling of the subsystem excitation manifolds in a fully coupled FDE scheme generally hinders the inclusion of the dynamical response of the entire environment in large complexes, 24 but allows in a truncated form to describe a few strongly coupled local excitations as relevant for chromophoric aggregates.…”

Section: Introductionmentioning

confidence: 99%

A quantum-mechanical perspective on linear response theory within polarizable embedding

List

Norman

Kongsted

et al. 2017

The Journal of Chemical Physics

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We present a derivation of linear response theory within polarizable embedding starting from a rigorous quantum-mechanical treatment of a composite system. To this aim, two different subsystem decompositions (symmetric and nonsymmetric) of the linear response function are introduced and the pole structures as well as residues of the individual terms are discussed. In addition to providing a thorough justification for the descriptions used in polarizable embedding models, this theoretical analysis clarifies which form of the response function to use and highlights complications in separating out subsystem contributions to molecular properties. The basic features of the presented expressions and various approximate forms are illustrated by their application to a composite model system.

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“…[23] Finally, the PE model has been combined with a number of electronic-structure methods including Hartree-Fock (HF) and Kohn-Sham density functional theory (DFT) [10,11] but also correlated wave-function-based methods such as coupled cluster (CC), [24,25] multiconfigurational self-consistent-field theory, [26] multiconfigurational short-range DFT, [27] the second-order polarization propagator approach [28] and also in a relativistic framework using DFT. [29] For a recent perspective on the PE model, we refer to Reference [30]. The user is thus able to choose among different electronic-structure methods and select the one that is known to perform best from a cost-efficiency point of view for a given property.…”

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confidence: 99%

Response properties of embedded molecules through the polarizable embedding model

Steinmann

Reinholdt

Nørby

et al. 2018

Int J of Quantum Chemistry

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The polarizable embedding (PE) model is a fragment-based quantum-classical approach aimed at accurate inclusion of environment effects in quantum-mechanical response property calculations. The aim of this tutorial review is to give insight into the practical use of the PE model.Starting from a set of molecular structures and until you arrive at the final property, there are many crucial details to consider in order to obtain trustworthy results in an efficient manner. To lower the threshold for new users wanting to explore the use of the PE model, we describe and discuss important aspects related to its practical use. This includes directions on how to generate input files and how to run a calculation. K E Y W O R D S computational spectroscopy, molecular properties, polarizable embedding, QM/MM, response properties 1 | INTRODUCTION Hybrid quantum-classical approaches for modeling of chemical or biological systems have in recent years gained considerable interest. The reasonfor such popularity of these models relies, to a large degree, on their efficiency and the fact that such models enable calculations on systems of sizes that are otherwise impossible using pure quantum-mechanical methods. The dielectric continuum models belong to the simplest of the quantum-classical approaches, [1,2] and models like the polarizable continuum model [3,4] are today implemented in many of the available electronic-structure programs. In addition, such models are very easy to use: based on a predefined set of atomic radii and the dielectric constant of the solvent, the user can include solvation effects based only on a single calculation. Only one calculation is needed because the dielectric continuum models implicitly include sampling of solvent configurations. On the other hand, it is well-known that the dielectric continuum models possess several drawbacks, such as the inability to model the directionality of specific intermolecular interactions like hydrogen bonding or π-π stacking. Because of this, modeling of environment anisotropies, as found in, for example, protein matrices is lost.Another class of quantum-classical approaches consists of discrete models where the atomistic detail of the environment is kept, that is, models based on the concept of combined quantum mechanics and molecular mechanics (QM/MM). [5][6][7][8] Discrete models, compared to the dielectric continuum models, realistically describe the environment, but at an increased level of both complexity and computational requirements.Regarding the latter point, the increase in computational time is not linked to the discrete nature of the environment as such but rather that

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Excited states in large molecular systems through polarizable embedding

Cited by 87 publications

References 134 publications

Modeling absorption spectra of molecules in solution

Modeling absorption spectra of molecules in solution

A quantum-mechanical perspective on linear response theory within polarizable embedding

Response properties of embedded molecules through the polarizable embedding model

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