COSMO-RI-ADC(2) excitation energies and excited state gradients

Khani, Sarah Karbalaei; Khah, Alireza Marefat; Hättig, Christof

doi:10.1039/c8cp00643a

Cited by 37 publications

(43 citation statements)

References 40 publications

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“…The solvent effect has been included using the COSMO approach in combination with the RI‐ADC(2) method as implemented in Turbomole which captures all solvent effects on excited state energies at the linear response (LR) level 34 . Five different solvents (ethanol, methanol, cyclohexane, hexane, and dicloromethane) have been used as in the experiments.…”

Section: Methodsmentioning

confidence: 99%

Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families

Feldt¹,

Brown

2020

J Comput Chem

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It was previously reported that Laplace transformed local CC2 (LCC2*) provided the best agreement (MAE = 0.145 eV) when comparing vertical excitation energies to experimental λ max for a benchmark set of 17 BODIPY/Aza-BODIPY molecules. However, these energies did not agree with values obtained from canonical CC2. Here we report LCC2* computations of vertical excitation energies on the same benchmark set of molecules using a newly implemented treatment of the ground state. Comparison with resolution-of-identity approximate coupled cluster to second-order (RI-CC2) results demonstrate that the new LCC2* results agree quantitatively. Furthermore, these values can easily be corrected empirically to also provide excellent agreement with the experiment. We show that the local algebraic diagrammatic construction to second-order (LADC(2)) method exhibits the same differences between implementations as seen for LCC2. The source of the difference is traced to an improved treatment of the ground state in the local methods, which decreases agreement with the experiment (as attributed to a fortuitous cancellation of errors) but significantly improves agreement with RI-CC2. While the absolute vertical excitation energies now show larger deviations, there remains a strong linear correlation between the LCC2* results and the experiment. For the 17 BODIPY/Aza-BODIPY molecules vertical excitation energies are determined using DLPNO-STEOM-CCSD and shown to have excellent agreement with experimental λ max (MAE = 0.145 eV), which is the best of all the single-reference methods. The vertical excitation energies are determined using LCC2*, empirically corrected LCC2*, and RI-CC2 for a series of eight large BODIPYs and Aza-BODIPYs.

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Section: Methodsmentioning

confidence: 99%

Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families

Feldt¹,

Brown

2020

J Comput Chem

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“…v ia , bj COSMO is the potential energy contribution of the implicit conductor-like screening model (COSMO) used to incorporate effects of the chemical surrounding. 32 , 33 The COSMO term is convenient, as it is far more efficient to describe the surrounding by a polarizable medium, modeled by its dielectric function and the refractive index, instead of adding further atomistic regions to the ab initio DFT region. For a detailed discussion of COSMO, we refer the reader to ref ( 32 ).…”

Section: Methodsmentioning

confidence: 99%

Multiscale Modeling of Broadband Perfect Absorbers Based on Gold Metallic Molecules

2022

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The modeling of functional photonic devices that rely on molecular materials continues to be a major contemporary challenge. It is a challenge because, in the Maxwell equations, which govern the light-matter interaction, material properties are primarily introduced on phenomenological grounds and not from first principles. To overcome such limitations, we outline a multiscale modeling approach that bridges multiple length scales. We can predict with our approach the optical response of a photonic device that exploits in its design molecular materials whose properties were determined using time-dependent density functional theory. The specifically considered device is a broadband perfect absorber that uses in part a thin film comprising gold molecules made from 144 atoms. Our methodology discloses various chemical and physical effects that define such a device’s response. Our methodology is versatile, and a larger number of applications will profit from this development.

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“…In particular, the latter depends on the transition density of the solute and can be recommended for the description of transition properties, while in the former approach the solvent responds to the excited state density of the solute and thus it is also called state specific since for each state it provides a better description of the mutual polarization between solute and solvent . A different implicit solvent model, the conductor‐like screening model (COSMO) was also implemented for the ADC(2) method recently . While implicit solvent models are much cheaper than explicit ones, they fail to capture specific interactions with the environment, such as hydrogen bonds between solute and solvent.…”

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

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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COSMO-RI-ADC(2) excitation energies and excited state gradients

Cited by 37 publications

References 40 publications

Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families

Assessment of local coupled cluster methods for excited states of BODIPY/Aza‐BODIPY families

Multiscale Modeling of Broadband Perfect Absorbers Based on Gold Metallic Molecules

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

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