Pressure-dependent electronic structure calculations using integral equation-based solvation models

Pongratz, Tim; Kibies, Patrick; Eberlein, Lukas; Tielker, Nicolas; Hölzl, Christoph; Imoto, Sho; Erlach, Markus Beck; Kurrmann, Simon; Schummel, Paul Hendrik; Hofmann, Martin; Reiser, Oliver; Winter, Roland; Kremer, Werner; Kalbitzer, Hans Robert; Marx, Dominik; Horinek, Dominik

doi:10.1016/j.bpc.2019.106258

Cited by 16 publications

(26 citation statements)

References 74 publications

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“…Pongratz et al have suggested a solution for this problem using the 1D-RISM approximation to account for nonequilibrium effects. 63 But we note that they calculate the vibrational frequencies from displacements along normal modes obtained from a PCMbased stationary point. In the present implementation everything is calculated self-consistently, but the limitations regarding the missing coupling between solvent and solute vibrational modes persist at this point in time.…”

Section: ■ Theorymentioning

confidence: 99%

“…Solvent Effects on 17 O Shieldings/Shifts of N-Methylformamide. Kast and co-workers recently were the first to apply 3D-RISM-SCF to NMR shifts in solution, in particular to 1 H, 13 C, and 15 N shifts of N-methylacetamide in water 45 (including pressure dependencies of solution shifts 46,47,63 ). We have seen above in the context of solvatochromism that water is a rather special solvent within a RISM framework, not necessarily the best-suited case (see also below).…”

Section: ■ Computational Detailsmentioning

confidence: 99%

“…We note recent attempts to approximately account for some degree of nonequilibrium solvation in pressure-dependent vibrational calculations using EC-RISM. 63 That work tried to circumvent numerical problems for the displaced structures by freezing the 3D-RISM distribution functions for the equilibrium structure and using the resulting point charges in a 1D-RISM setting for symmetrical displacements along the normal modes of a prior PCM-based calculation. This ansatz was able to improve the pressure-induced shifts of certain frequencies notably but was not found to provide consistent results for all modes.…”

Section: ■ Computational Detailsmentioning

confidence: 99%

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Evaluation of an Efficient 3D-RISM-SCF Implementation as a Tool for Computational Spectroscopy in Solution

Reimann

Kaupp

2020

J. Phys. Chem. A

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The 3D-RISM-SCF solvent-model implementation of Gusarov et al. [J. Phys. Chem. A 2006, 110, 6083−6090] in the Amsterdam density functional program has been improved and extended. In particular, an accurate yet efficient representation of the solute electrostatic potential is provided. The Coulombpotential fitting of many DFT codes can be used advantageously in this context. The extra effort compared to a point-charge representation is small for a given SCF cycle and compensated by faster SCF convergence. This allows applications to large solutes, as demonstrated by evaluation of the solvatochromism of Reichardt's dye. In general, TDDFT applications to excitation energies in solution stand out and are highlighted. Applications to the 17 O NMR chemical shifts of N-methylformamide in different solvents also demonstrate the distinct advantages of 3D-RISM over continuum solvents. Limitations are observed in this case for water solvent, where the solvent shielding is overestimated. This shortcoming applies also to the 17 O gas-to-liquid shift of water, where we used localized molecular orbital analyses for a deeper understanding. For such cases of extremely strong solute−solvent interactions, couplings between solute and solvent orbitals induced by the magnetic perturbation are relevant. These clearly require a quantum-mechanical treatment of the most closely bound solvent molecules. Except for such extreme cases, 3D-RISM-SCF is very well suited to treat solvent effects on NMR parameters. More serious limitations pertain to the treatment of vibrational spectra, where the absence of the coupling between solute and solvent vibrational modes limits the accuracy of applications of 3D-RISM-SCF. The reported extended, efficient, and numerically accurate 3D-RISM-SCF implementation should provide a useful tool to study chemical and spectroscopic properties of molecules of appreciable size in a realistic solvent environment.

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Section: ■ Theorymentioning

confidence: 99%

Section: ■ Computational Detailsmentioning

confidence: 99%

Section: ■ Computational Detailsmentioning

confidence: 99%

See 1 more Smart Citation

Evaluation of an Efficient 3D-RISM-SCF Implementation as a Tool for Computational Spectroscopy in Solution

Reimann

Kaupp

2020

J. Phys. Chem. A

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“…In ab initio molecular dynamics simulations, the challenges are typically overcome through the application of artificial biases or constraints and vast amounts of computational power [21,22]. Static quantum-chemical calculations often resort to combinations with continuum theories and classical models [23][24][25][26][27][28], tainting the first principles character of the calculation.…”

Section: Introductionmentioning

confidence: 99%

The Ionic Product of Water in the Eye of the Quantum Cluster Equilibrium

Kirchner¹,

Ingenmey

Domaros

et al. 2022

Molecules

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The theoretical description of water properties continues to be a challenge. Using quantum cluster equilibrium (QCE) theory, we combine state-of-the-art quantum chemistry and statistical thermodynamic methods with the almost historical Clausius–Clapeyron relation to study water self-dissociation and the thermodynamics of vaporization. We pay particular attention to the treatment of internal rotations and their impact on the investigated properties by employing the modified rigid-rotor–harmonic-oscillator (mRRHO) approach. We also study a novel QCE parameter-optimization procedure. Both the ionic product and the vaporization enthalpy yield an astonishing agreement with experimental reference data. A significant influence of the mRRHO approach is observed for cluster populations and, consequently, for the ionic product. Thermodynamic properties are less affected by the treatment of these low-frequency modes.

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“…These are applied in the QC calculations from which, after convergence of an iterative cycle, the wave function of the solute in solution as well as the excess chemical potential at infinite dilution and other properties of the fully polarized solute can be determined [12,13]. As usual, we took the sum of the polarized electronic energy and the excess chemical potential as an estimate of the Gibbs energy of the molecule in solution to calculate derived properties such as solvation Gibbs energies (by referencing to a gas phase calculation), acidity constants, partition and distribution coefficients, or tautomer and conformational populations of molecules under ambient and extreme conditions in a variety of solvents [14][15][16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

The SAMPL6 challenge on predicting octanol–water partition coefficients from EC-RISM theory

Tielker

Tomazic

Eberlein

et al. 2020

J Comput Aided Mol Des

Self Cite

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Results are reported for octanol-water partition coefficients (log P) of the neutral states of drug-like molecules provided during the SAMPL6 (Statistical Assessment of Modeling of Proteins and Ligands) blind prediction challenge from applying the "embedded cluster reference interaction site model" (EC-RISM) as a solvation model for quantum-chemical calculations. Following the strategy outlined during earlier SAMPL challenges we first train 1-and 2-parameter water-free ("dry") and water-saturated ("wet") models for n-octanol solvation Gibbs energies with respect to experimental values from the "Minnesota Solvation Database" (MNSOL), yielding a root mean square error (RMSE) of 1.5 kcal mol −1 for the best-performing 2-parameter wet model, while the optimal water model developed for the pK a part of the SAMPL6 challenge is kept unchanged (RMSE 1.6 kcal mol −1 for neutral compounds from a model trained on both neutral and ionic species). Applying these models to the blind prediction set yields a log P RMSE of less than 0.5 for our best model (2-parameters, wet). Further analysis of our results reveals that a single compound is responsible for most of the error, SM15, without which the RMSE drops to 0.2. Since this is the only compound in the challenge dataset with a hydroxyl group we investigate other alcohols for which Gibbs energy of solvation data for both water and n-octanol are available in the MNSOL database to demonstrate a systematic cause of error and to discuss strategies for improvement.

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Pressure-dependent electronic structure calculations using integral equation-based solvation models

Cited by 16 publications

References 74 publications

Evaluation of an Efficient 3D-RISM-SCF Implementation as a Tool for Computational Spectroscopy in Solution

Evaluation of an Efficient 3D-RISM-SCF Implementation as a Tool for Computational Spectroscopy in Solution

The Ionic Product of Water in the Eye of the Quantum Cluster Equilibrium

The SAMPL6 challenge on predicting octanol–water partition coefficients from EC-RISM theory

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