A ΔSCF model for excited states within a polarisable embedding

Nottoli, Michele; Mazzeo, Patrizia; Lipparini, Filippo; Cupellini, Lorenzo; Mennucci, Benedetta

doi:10.1080/00268976.2022.2089605

Cited by 5 publications

(14 citation statements)

References 46 publications

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“…The CT states were described using ΔSCF coupled with AMOEBA . Initial guesses were obtained by moving one electron from the π Tyr to the π FMN * orbital.…”

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confidence: 99%

“…18 Thus, ΔSCF is a promising strategy for dealing with ES dynamics that occur on a single diabatic surface, but extensions to nonadiabatic dynamics have been presented as well. 19,20 Recently we have presented the coupling of ΔSCF methods to a polarizable MM embedding 21 using the popular AMOEBA force field. 22 The latter employs fixed charges, dipoles, and quadrupoles to describe the electrostatics and an inducedpoint-dipole (IPD) model to describe polarization.…”

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confidence: 99%

“…Recently we have presented the coupling of ΔSCF methods to a polarizable MM embedding 21 using the popular AMOEBA force field. 22 The latter employs fixed charges, dipoles, and quadrupoles to describe the electrostatics and an induced-point-dipole (IPD) model to describe polarization.…”

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confidence: 99%

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Fast Method for Excited-State Dynamics in Complex Systems and Its Application to the Photoactivation of a Blue Light Using Flavin Photoreceptor

Mazzeo

Hashem

Lipparini

et al. 2023

J. Phys. Chem. Lett.

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The excited-state dynamics of molecules embedded in complex (bio)matrices is still a challenging goal for quantum chemical models. Hybrid QM/MM models have proven to be an effective strategy, but an optimal combination of accuracy and computational cost still has to be found. Here, we present a method which combines the accuracy of a polarizable embedding QM/MM approach with the computational efficiency of an excited-state self-consistent field method. The newly implemented method is applied to the photoactivation of the blue-light-using flavin (BLUF) domain of the AppA protein. We show that the proton-coupled electron transfer (PCET) process suggested for other BLUF proteins is still valid also for AppA.

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“…The CT states were described using ΔSCF coupled with AMOEBA . Initial guesses were obtained by moving one electron from the π Tyr to the π FMN * orbital.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Fast Method for Excited-State Dynamics in Complex Systems and Its Application to the Photoactivation of a Blue Light Using Flavin Photoreceptor

Mazzeo

Hashem

Lipparini

et al. 2023

J. Phys. Chem. Lett.

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“…It is sometimes tacitly assumed that the difference between LR and SS excitation energies already present in vacuum cancels when calculating the solvent shift so that any observed difference in the shift must be solely due to the effect of the dynamical polarization of the environment, described by eqs and . For example, in a recent paper comparing LR-DFT and ΔSCF (an SS formulation of DFT) shifts of a dark state of dimethylaminobenzonitrile, a discrepancy between the calculated difference between LR and SS shifts and the difference expected from the application of eqs and was ascribed to the perturbative nature of these equations. It is possible that the discrepancy can instead be explained by the different reactions of LR and SS excitation energies to the static part of the environment potential.…”

Section: Resultsmentioning

confidence: 99%

“…However, when combined with polarizable environment models, LR and SS methods will generally predict different transition energies, even if the corresponding QM equations could be solved exactly. In previous studies, − much attention has been paid to this difference, which is caused by the different couplings of the LR and SS methods to the polarizable part of the environment potential (see eqs and and the accompanying discussion below).…”

Section: Introductionmentioning

confidence: 99%

Multiconfigurational SCF and Short-Range DFT Combined with Polarizable Density Embedding: Comparison of Linear-Response and State-Specific Solvatochromic Shifts of Acrolein and Para-nitrophenolate in Water

Heuvel

Reinholdt

Jensen

et al. 2022

J. Chem. Theory Comput.

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The polarizable density embedding model is combined with the multiconfigurational self-consistent field and MC-srDFT electronic structure methods to calculate solvatochromic shifts of the n−π* absorption of acrolein and the π–π* absorption of the para-nitrophenolate anion in aqueous solution. Differences between linear-response (LR) and state-specific (SS) solvent shifts are analyzed by assessing the contributions of different terms in the solvent potential. This comparison shows that the differences are not only due to the intrinsically different response of LR and SS excitation energies to the polarizability of the environment but also due to a different response to the static part of the environment potential. These observations show that even in nonpolarizable environments, LR and SS calculations based on SCF (orbital optimization) methods do not necessarily agree on the spectral shift. The difference can be as large as, or even dominate, the difference due to dynamical polarization.

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QM/AMOEBA description of properties and dynamics of embedded molecules

Nottoli

Bondanza

Mazzeo

et al. 2023

WIREs Comput Mol Sci

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We describe the development, implementation, and application of a polarizable QM/MM strategy, based on the AMOEBA polarizable force field, for calculating molecular properties and performing dynamics of molecular systems embedded in complex matrices. We show that polarizable QM/MM is a well‐understood, mature technology that can be deployed using a state‐of‐the‐art implementation that combines efficient numerical methods and linear scaling techniques. Thanks to these numerical advances and to the availability of parameters for a wide manifold of systems in the AMOEBA force field, polarizable QM/AMOEBA can be used for advanced production applications, that range from the prediction of spectroscopies to ground‐ and excited‐state multiscale ab initio molecular dynamics simulations.This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Electronic Structure Theory > Combined QM/MM Methods

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A ΔSCF model for excited states within a polarisable embedding

Cited by 5 publications

References 46 publications

Fast Method for Excited-State Dynamics in Complex Systems and Its Application to the Photoactivation of a Blue Light Using Flavin Photoreceptor

Fast Method for Excited-State Dynamics in Complex Systems and Its Application to the Photoactivation of a Blue Light Using Flavin Photoreceptor

Multiconfigurational SCF and Short-Range DFT Combined with Polarizable Density Embedding: Comparison of Linear-Response and State-Specific Solvatochromic Shifts of Acrolein and Para-nitrophenolate in Water

QM/AMOEBA description of properties and dynamics of embedded molecules

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