Embedding Methods in Quantum Chemistry

Goez, Albrecht; Neugebauer, Johannes

doi:10.1007/978-981-10-5651-2_7

Cited by 35 publications

(36 citation statements)

References 295 publications

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“…A related way to also account for specific solute-solvent interactions is through the use of an embedding potential. [53][54][55] Embedding methods allow a system treated with a high-level of theory to experience the potential of an environment treated with a lower level of theory, enabling the QM treatment of large amounts of solvent around a solute. [56] The embedding approach has been extended to response theory, [57,58] allowing the calculation of excitation energies within the field of many solvent molecules.…”

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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“…This field is in itself an area of active research and we will only discuss the most important recent developments in the special case when the central system is treated using some excited state CC method. The interested reader is referred to the comprehensive review of Goez and Neugebauer for further details …”

Section: Algorithmic Approximationsmentioning

confidence: 99%

Single‐reference coupled cluster methods for computing excitation energies in large molecules: The efficiency and accuracy of approximations

Izsák

2019

WIREs Comput Mol Sci

100

110

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While methodological developments in the last decade made it possible to compute coupled cluster (CC) energies including excitations up to a perturbative triples correction for molecules containing several hundred atoms, a similar breakthrough has not yet been reported for excited state computations. Accurate CC methods for excited states are still expensive, although some promising candidates for an efficient and accurate excited state CC method have emerged recently. This review examines the various approximation schemes with particular emphasis on their performance for excitation energies and summarizes the best state-of-the-art results which may pave the way for a robust excited state method applicable to molecules of hundreds of atoms.Among these, special attention will be given to exploiting the techniques of similarity transformation, perturbative approximations as well as integral decomposition, local and embedding techniques within the equation of motion CC framework. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Structure and Mechanism > Molecular Structures K E Y W O R D S accuracy, coupled cluster, efficiency, excited states, single reference | INTRODUCTIONIn their lucid review written a few years ago, 1 Sneskov and Christiansen discussed the various coupled cluster (CC) methods available for excited states. Using the systematic machinery of response theory, they described a hierarchy of methods, established a link between response theory and equation of motion (EOM) methods, and finished by discussing a number of approaches that might be used to reduce the computational cost. The present review aims at providing an overview of efficient methods available primarily for large molecules, and hence the emphasis will be laid more upon recent methodological advances which reduce the cost and on the extent this affects the accuracy of these methods. For ground state calculations, choosing a reference method for benchmarks is quite easy, since the CC singles doubles and perturbative triples, or CCSD(T), ansatz 2 is not only widely regarded as the gold standard of quantum chemistry, but it has also recently become possible to compute CCSD(T) energies for molecules containing several hundred atoms. 3 For excited states, progress has been

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“…The mutual interaction between the fragments can be realized via a perturbation theory approach, where each fragment perturbs the other ones via its electrostatic potential (acting as a perturbation potential) . Following these ideas, many embedding or subsystem density functional theory (DFT) methods like frozen density embedding or embedded correlated wave functions methods were developed in the literature.…”

Section: Application Of Theorem 1 and 2 To The Linear Density‐densitymentioning

confidence: 99%

Efficient representation of the linear density‐density response function

et al. 2019

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We present a thorough derivation of the mathematical foundations of the representation of the molecular linear electronic density-density response function in terms of a computationally highly efficient moment expansion. Our new representation avoids the necessities of computing and storing numerous eigenfunctions of the response kernel by means of a considerable dimensionality reduction about from 10 3 to 10 1 . As the scheme is applicable to any compact, self-adjoint, and positive definite linear operator, we present a general formulation, which can be transferred to other applications with little effort. We also present an explicit application, which illustrates the actual procedure for applying the moment expansion of the linear density-density response function to a water molecule that is subject to a varying external perturbation potential.

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Embedding Methods in Quantum Chemistry

Cited by 35 publications

References 295 publications

Modeling absorption spectra of molecules in solution

Modeling absorption spectra of molecules in solution

Single‐reference coupled cluster methods for computing excitation energies in large molecules: The efficiency and accuracy of approximations

Efficient representation of the linear density‐density response function

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