Analytical calculation of pressure for confined atomic and molecular systems using the eXtreme‐Pressure Polarizable Continuum Model

Cammi, Roberto; Chen, Bo; Rahm, Martin

doi:10.1002/jcc.25544

Cited by 28 publications

(36 citation statements)

References 57 publications

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“…Pressure is excerted on the atom by the spatial overlap of the atom's electron density with the electron density of the medium. The pressure is computed as the derivative of the electronic energy

G

of the compressed atom with respect to the volume

V_{c}

of the confining cavity: [106]

true p = - ((), \frac{\partial G}{\partial V_{c}}) .

…”

Section: Methodsmentioning

confidence: 99%

Non‐Bonded Radii of the Atoms Under Compression

et al. 2020

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We present quantum mechanical estimates for non‐bonded, van der Waals‐like, radii of 93 atoms in a pressure range from 0 to 300 gigapascal. Trends in radii are largely maintained under pressure, but atoms also change place in their relative size ordering. Multiple isobaric contractions of radii are predicted and are explained by pressure‐induced changes to the electronic ground state configurations of the atoms. The presented radii are predictive of drastically different chemistry under high pressure and permit an extension of chemical thinking to different thermodynamic regimes. For example, they can aid in assignment of bonded and non‐bonded contacts, for distinguishing molecular entities, and for estimating available space inside compressed materials. All data has been made available in an interactive web application.

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G

of the compressed atom with respect to the volume

V_{c}

of the confining cavity: [106]

true p = - ((), \frac{\partial G}{\partial V_{c}}) .

…”

Section: Methodsmentioning

confidence: 99%

Non‐Bonded Radii of the Atoms Under Compression

et al. 2020

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“…To describe molecules at extreme pressure, Cammi and coworkers [28][29][30] proposed the XP-PCM method, where the free energy of the system at the given pressure p is…”

Section: Theorymentioning

confidence: 99%

“…Its accuracy in describing high-pressure phenomena is highly dependent on the force field parameterization, 24 and could lead to results contradicting experimental findings. [25][26][27] The extreme pressure polarizable continuum model (XP-PCM) by Cammi and co-workers [28][29][30] emerges as a computationally efficient approach to incorporate pressure effects (on the order of GPa 29 ) into quantum chemistry calculations on single molecules. It has been applied to the study of small to medium size molecules from single atoms, [30][31][32] small organic molecules, 29,33 to crys-tals 34,35 and fullerenes.…”

Section: Introductionmentioning

confidence: 99%

“…[25][26][27] The extreme pressure polarizable continuum model (XP-PCM) by Cammi and co-workers [28][29][30] emerges as a computationally efficient approach to incorporate pressure effects (on the order of GPa 29 ) into quantum chemistry calculations on single molecules. It has been applied to the study of small to medium size molecules from single atoms, [30][31][32] small organic molecules, 29,33 to crys-tals 34,35 and fullerenes. 36 While XP-PCM DFT calculations are much more efficient than their periodic DFT counterparts, 35 their applications in quantum chemistry calculation of large molecular and biomolecular systems are still hampered by the high computational overhead for evaluating large numbers of related electron integrals.…”

Section: Introductionmentioning

confidence: 99%

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Quantum Chemistry for Molecules at Extreme Pressure on Graphical Processing Units: Implementation of Extreme Pressure Polarizable Continuum Model

Gale¹,

Hruska²,

Liu

2021

Preprint

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<p>Pressure plays essential roles in chemistry by altering structures and controlling chemical reactions. The extreme-pressure polarizable continuum model (XP-PCM) is an emerging method with an efficient quantum mechanical description of molecules at high pressure (on the order of GPa), but its application to large molecular systems was previously hampered by CPU computation bottleneck. Here, we exploit advances in Graphical Processing Units (GPUs) to accelerate XP-PCM calculations and enable quantum chemistry simulation of large molecular and biomolecular systems under high pressure. We benchmarked the performance using 18 small proteins in aqueous solutions. Using a single GPU, our method evaluates the density functional theory (DFT) single point energy of a protein with over 500 atoms and 4000 basis functions under extreme pressure within half an hour. The time taken by the XP-PCM-integral evaluation is typically 1% of the time taken for a gas phase DFT calculation on the same system. The overall XP-PCM calculations require less computational effort than that for their gas-phase counterpart due to the improved convergence of self-consistent field iterations. Therefore, the description of the high-pressure effects with our GPU accelerated XP-PCM is feasible for any molecule tractable for gas-phase DFT calculation. To validate the accuracy of our method, we evaluated the free energy of argon, whose properties under high pressure are known from experiments. The pressure-volume relationship predicted by our method matches previous theoretical and experimental results.</p>

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“…An analytic calculation of the pressure in XP-PCM has been described in detail recently. [37] The XP-PCM approach has been successfully used to calculate Gibbs energy profiles of the Diels-Alder reaction between cyclopentadiene and ethylene at different pressures ( Figure 2). [7] It has been found that the reaction becomes almost barrierless at 3.0 GPa and that the transition state disappears altogether at around 11.2 GPa.…”

Section: Extreme Pressure Polarizable Continuum Modelmentioning

confidence: 99%

Quantum chemical modeling of molecules under pressure

Stauch

2020

Int J of Quantum Chemistry

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Pressure can be used to initiate a plethora of intriguing transformations and chemical reactions. During the past 10 years or so, several quantum chemical methods have been developed that describe the structural and electronic changes in molecules under pressure. This perspective focuses on three of these methods: the extreme pressure polarizable continuum model, the generalized force-modified potential energy surface, and the hydrostatic compression force field approach. The theoretical background of each method is discussed, and several interesting applications are reviewed. The challenges that the field faces, as well as possible routes for future developments, are pointed out.

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Analytical calculation of pressure for confined atomic and molecular systems using the eXtreme‐Pressure Polarizable Continuum Model

Cited by 28 publications

References 57 publications

Non‐Bonded Radii of the Atoms Under Compression

Non‐Bonded Radii of the Atoms Under Compression

Quantum Chemistry for Molecules at Extreme Pressure on Graphical Processing Units: Implementation of Extreme Pressure Polarizable Continuum Model

Quantum chemical modeling of molecules under pressure

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