Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes

Stauch, Tim; Chakraborty, Romit; Head‐Gordon, Martin

doi:10.26434/chemrxiv.9741434

“…In this paper, an electronic structure method for geometry optimizations and AIMD sim- In the future, it is planned to use GOSTSHYP for the simulation of metal centers under pressure and test the applicability of the method to reproduce pressure-induced spin crossover processes, 85,86,95 which will contribute to the development of novel storage materials for gases, energy and memory. It will be particularly interesting to compare the performances of GOSTSHYP and mechanochemical models of pressure, 46,51,52 since GOSTSHYP is expected to describe pressure-induced changes in electronic configuration more accurately due to the explicit description of electron density compression. Moreover, a wider range of pressure-induced chemical reactions will be tested with GOSTSHYP in the future with the aim of suggesting new synthetic routes in organic chemistry and beyond.…”

Section: Discussionmentioning

confidence: 99%

“…However, pressures of several TPa are irrelevant for applications in chemical laboratories, given that pressures in the range of a few hundred GPa are available experimentally today. 4 The ability to apply hydrostatic pressure to atoms distinguishes GOSTSHYP from the mechanochemical models of pressure, 46,51,52 which require at least two atoms to work, and emphasizes the connection between GOSTSHYP and XP-PCM, [53][54][55] which also allows for the treatment of single atoms.…”

Section: Dependence On Adjustable Parametersmentioning

confidence: 99%

Modeling Molecules Under Pressure with Gaussian Potentials

Scheurer¹,

Dreuw²,

Epifanovsky³

et al. 2020

Preprint

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<div> <div> <div> <p>The computational modeling of molecules under high pressure is a growing research area that augments experimental high-pressure chemistry. Here, a new electronic structure method for modeling atoms and molecules under pressure, the <i>Gaussians On Sur</i><i>ace Tesserae Simulate HYdrostatic Pressure</i> (GOSTSHYP) approach, is introduced. In this method, a set of Gaussian potentials is distributed evenly on the van der Waals surface of the investigated chemical system, leading to a compression of the electron density and the atomic scaffold. Since no parameters other than the pressure need to be specified, GOSTSHYP allows straightforward geometry optimizations and <i>ab initio</i> Molecular Dynamics simulations of chemical systems under pressure for non-expert users. Calculated energies, bond lengths and dipole moments under pressure fall within the range of established computational methods for high-pressure chemistry. A Diels-Alder reaction and the cyclotrimerization of acetylene showcase the ability of GOSTSHYP to model pressure-induced chemical reactions. The connection to mechanochemistry is pointed out. </p> </div> </div> </div>

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“…To showcase the difference between X-HCFF and HCFF, an aliphatic molecule is compressed using both approaches. While HCFF was shown to deliver physically meaningful and chemically intuitive results for molecules that can be circumscribed onto a sphere, 31 the method performs poorly for butane under a pressure of 50 GPa (Figure 2): Since strong forces point towards the molecular centroid and these forces are strongest for the outermost atoms, the molecule tends to minimize its surface and folds into a HCFF:…”

Section: Comparison Between X-hcff and Hcffmentioning

confidence: 99%

A Mechanochemical Model for the Simulation of Molecules and Molecular Crystals Under Hydrostatic Pressure

Stauch

¹

2020

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<div> <div> <div> <p>A novel mechanochemical method for the simulation of molecules and molecular crystals under hydrostatic pressure, the eXtended Hydrostatic Compression Force Field (X-HCFF) approach, is introduced. In contrast to comparable methods, the desired pressure can be adjusted non-iteratively and molecules of general shape retain chemically reasonable geometries even at high pressures. The implementation of the X-HCFF approach is straightforward and the computational cost is practically the same as for a regular geometry optimization. Pressure can be applied by using any desired electronic structure method for which a nuclear gradient is available. The results of X-HCFF for pressure-dependent intramolecular structural changes in the investigated molecules and molecular crystals as well as a simple pressure-induced dimerization reaction are chemically intuitive and fall within the range of other established computational methods. Experimental spectroscopic data of a molecular crystal under pressure are reproduced accurately. </p> </div> </div> </div>

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“…The G-FMPES method has been applied to model chemical reactions under pressure 49,50 and investigate pressure-induced changes in vibrational frequencies. 46 An extension of the G-FMPES approach, the Hydrostatic Compression Force Field (HCFF), has been proposed recently 51 and was used to model pressure-induced spin crossover phenomena. In HCFF, the definitions of the surface area and the applied pressure are changed in comparison to G-FMPES.…”

Section: Introductionmentioning

confidence: 99%

Modeling Molecules Under Pressure with Gaussian Potentials

Scheurer

¹

,

Dreuw

²

,

Epifanovsky

³

et al. 2020

Preprint

Self Cite

View full text Add to dashboard Cite

<div> <div> <div> <p>The computational modeling of molecules under high pressure is a growing research area that augments experimental high-pressure chemistry. Here, a new electronic structure method for modeling atoms and molecules under pressure, the <i>Gaussians On Sur</i><i>ace Tesserae Simulate HYdrostatic Pressure</i> (GOSTSHYP) approach, is introduced. In this method, a set of Gaussian potentials is distributed evenly on the van der Waals surface of the investigated chemical system, leading to a compression of the electron density and the atomic scaffold. Since no parameters other than the pressure need to be specified, GOSTSHYP allows straightforward geometry optimizations and <i>ab initio</i> Molecular Dynamics simulations of chemical systems under pressure for non-expert users. Calculated energies, bond lengths and dipole moments under pressure fall within the range of established computational methods for high-pressure chemistry. A Diels-Alder reaction and the cyclotrimerization of acetylene showcase the ability of GOSTSHYP to model pressure-induced chemical reactions. The connection to mechanochemistry is pointed out. </p> </div> </div> </div>

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Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes

Cited by 7 publications

References 27 publications

Modeling Molecules Under Pressure with Gaussian Potentials

Modeling Molecules Under Pressure with Gaussian Potentials

A Mechanochemical Model for the Simulation of Molecules and Molecular Crystals Under Hydrostatic Pressure

Modeling Molecules Under Pressure with Gaussian Potentials

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