Nuclear Magnetic Shielding Constants from Quantum Mechanical/Molecular Mechanical Calculations Using Polarizable Embedding: Role of the Embedding Potential

Steinmann, Casper; Olsen, Jógvan Magnus Haugaard; Kongsted, Jacob

doi:10.1021/ct400880n

Cited by 39 publications

(64 citation statements)

References 35 publications

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“…It has been successfully applied to model the environmental effects on both electric and magnetic molecular properties. 8,27,28 The aim of the present study is to broaden the scope of the PE model to vibrational properties of molecules embedded in large and complex environments. To this end, we have implemented molecular gradients with respect to nuclear displacements in the quantum region within the PE framework.…”

Section: Introductionmentioning

confidence: 99%

Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

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Beerepoot

Olsen

et al. 2015

The Journal of Chemical Physics

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We present an implementation of analytical quantum mechanical molecular gradients within the polarizable embedding (PE) model to allow for efficient geometry optimizations and vibrational analysis of molecules embedded in large, geometrically frozen environments. We consider a variational ansatz for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn-Sham density functional theory. As the first application of the implementation, we consider the internal vibrational Stark effect of the C==O group of acetophenone in different solvents and derive its vibrational linear Stark tuning rate using harmonic frequencies calculated from analytical gradients and computed local electric fields. Comparisons to PE calculations employing an enlarged quantum region as well as to a non-polarizable embedding scheme show that the inclusion of mutual polarization between acetophenone and water is essential in order to capture the structural modifications and the associated frequency shifts observed in water. For more apolar solvents, a proper description of dispersion and exchange-repulsion becomes increasingly important, and the quality of the optimized structures relies to a larger extent on the quality of the Lennard-Jones parameters. C 2015 AIP Publishing LLC. [http://dx

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Section: Introductionmentioning

confidence: 99%

Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

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Beerepoot

Olsen

et al. 2015

The Journal of Chemical Physics

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“…We have recently shown that the quality of the embedding potential has a profound impact on obtaining, e.g. converged NMR shielding constants 31 . In light of this, we here show the importance of utilizing an accurate embedding potential that is derived from first principles and which can reproduce the true quantum mechanical embedding potential and is not taken from a traditional protein force field.…”

Section: Introductionmentioning

confidence: 99%

Electronic Energy Transfer in Polarizable Heterogeneous Environments: A Systematic Investigation of Different Quantum Chemical Approaches

Steinmann

Kongsted

2015

J. Chem. Theory Comput.

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Theoretical prediction of transport and optical properties of protein-pigment complexes is of significant importance when aiming at understanding the structure-function relationship in such systems. Electronic energy transfer (EET) couplings represent a key property in this respect since such couplings provide important insight into the strength of interaction between photoactive pigments in protein-pigment complexes. Recently, attention has been payed to how the environment modifies or even controls the electronic couplings. To enable such theoretical predictions, a fully polarizable embedding model has been suggested (Curutchet, C., et al. J. Chem. Theory Comput., 2009, 5, 1838-1848). In this work, we further develop this computational model by extending it with an ab initio derived polarizable force field including higher-order multipole moments. We use this extended model to systematically examine three different ways of obtaining EET couplings in a heterogeneous medium ranging from use of the exact transition density to a point-dipole approximation. Several interesting observations are made, for example, the explicit use of transition densities in the calculation of the electronic couplings, and also when including the explicit environment contribution, can be replaced by a much simpler transition point charge description without comprising the quality of the model predictions.

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“…This has also been demonstrated in recent studies. In an investigation of solvent effects on nuclear magnetic shielding constants by Steinmann et al it was shown that the size of the quantum region can be substantially reduced when a high-quality embedding potential is used compared to standard solvent potentials 24. In addition, Schwabe et al demonstrated that electronic excitations in green fluorescent protein (GFP) can be accurately reproduced using polarizable embedding potentials when compared to full quantum-mechanical calculations 68.…”

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Accuracy of Protein Embedding Potentials: An Analysis in Terms of Electrostatic Potentials

Olsen

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Kristensen

et al. 2015

J. Chem. Theory Comput.

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Quantum-mechanical embedding methods have in recent years gained significant interest and may now be applied to predict a wide range of molecular properties calculated at different levels of theory. To reach a high level of accuracy in embedding methods, both the electronic structure model of the active region and the embedding potential need to be of sufficiently high quality. In fact, failures in quantum mechanics/molecular mechanics (QM/MM)-based embedding methods have often been associated with the QM/MM methodology itself; however, in many cases the reason for such failures is due to the use of an inaccurate embedding potential. In this paper, we investigate in detail the quality of the electronic component of embedding potentials designed for calculations on protein biostructures. We show that very accurate explicitly polarizable embedding potentials may be efficiently designed using fragmentation strategies combined with single-fragment ab initio calculations. In fact, due to the self-interaction error in Kohn-Sham density functional theory (KS-DFT), use of large full-structure quantum-mechanical calculations based on conventional (hybrid) functionals leads to less accurate embedding potentials than fragment-based approaches. We also find that standard protein force fields yield poor embedding potentials, and it is therefore not advisable to use such force fields in general QM/MM-type calculations of molecular properties other than energies and structures.

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Nuclear Magnetic Shielding Constants from Quantum Mechanical/Molecular Mechanical Calculations Using Polarizable Embedding: Role of the Embedding Potential

Cited by 39 publications

References 35 publications

Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

Electronic Energy Transfer in Polarizable Heterogeneous Environments: A Systematic Investigation of Different Quantum Chemical Approaches

Accuracy of Protein Embedding Potentials: An Analysis in Terms of Electrostatic Potentials

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