Predicting Structure of Molecular Crystals from First Principles

Podeszwa, Rafał; Rice, Betsy M.; Szalewicz, Krzysztof

doi:10.1103/physrevlett.101.115503

Cited by 147 publications

(168 citation statements)

References 35 publications

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“…4 Further estimates of three-body lattice energy contributions using symmetry-adapted perturbation theory based on densityfunctional descriptions of the monomers [SAPT(DFT)] [5][6][7][8][9][10][11][12] for crystalline benzene indicated that three-body effects contribute around 1.6 kcal mol −1 (or about 14% of the total lattice energy). 13 More recent studies 14,15 suggest that the majority of the three-body effects in crystalline benzene are due to three-body dispersion interactions, estimated to contribute 1.1 or 1.7 kcal mol −1 using the Axilrod-Teller-Muto expression (below).…”

Section: Introductionmentioning

confidence: 99%

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Kennedy

McDonald

DePrince

et al. 2014

The Journal of Chemical Physics

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Coupled-cluster theory including single, double, and perturbative triple excitations [CCSD(T)] has been applied to trimers that appear in crystalline benzene in order to resolve discrepancies in the literature about the magnitude of non-additive three-body contributions to the lattice energy. The present results indicate a non-additive three-body contribution of 0.89 kcal mol −1 , or 7.2% of the revised lattice energy of −12.3 kcal mol −1 . For the trimers for which we were able to compute CCSD(T) energies, we obtain a sizeable difference of 0.63 kcal mol −1 between the CCSD(T) and MP2 three-body contributions to the lattice energy, confirming that three-body dispersion dominates over three-body induction. Taking this difference as an estimate of three-body dispersion for the closer trimers, and adding an Axilrod-Teller-Muto estimate of 0.13 kcal mol −1 for long-range contributions yields an overall value of 0.76 kcal mol −1 for three-body dispersion, a significantly smaller value than in several recent studies.

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Section: Introductionmentioning

confidence: 99%

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Kennedy

McDonald

DePrince

et al. 2014

The Journal of Chemical Physics

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“…We note that the intermolecular angles found in the oligoacene crystal structures (approximately 50° to 80° depending on the oligoacene) lie near the least stable intermolecular interaction energies. This points to a limitation in the current analysis, suggesting that important terms are not fully accounted for in a two-body SAPT0 approach; [129][130][131][132] thus, models aiming to predict crystal packing need to go beyond such approaches. 133 The analysis of the non-covalent interaction energies of oligoacene dimers reveals the complexity of molecular crystal engineering, with the small energy differences among rather different configurations providing a clear picture of why polymorphism is such a common phenomenon in these systems.…”

Section: The Oligoacene Seriesmentioning

confidence: 99%

Noncovalent Interactions in Organic Electronic Materials

Ravva

Risko

Brédas

2017

Non-Covalent Interactions in Quantum Chemistry and Physics

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In this Chapter, we provide an overview of how noncovalent interactions, determined by the chemical structure of π-conjugated molecules and polymers, govern essential aspects of the electronic, optical, and mechanical characteristics of organic semiconductors. We begin by describing general aspects of materials design, including the wide variety of chemistries exploited to control the electronic and optical properties of these materials. We then discuss explicit examples of how the study of noncovalent interactions can provide deeper chemical insights that can improve the design of new generations of organic electronic materials.2

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“…[23][24][25][26][27][28][29][30][31][32] The polymorphism is governed by very subtle interactions, such as weak noncovalent bonds. In order to address the problem satisfactorily, theoretical methods must possess sufficient accuracy to reproduce such interactions.…”

Section: Introductionmentioning

confidence: 99%

Diffusion Monte Carlo Study of Para-Diiodobenzene Polymorphism Revisited

Hongo

Watson

Iitaka

et al. 2015

J. Chem. Theory Comput.

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We revisit our investigation of the diffusion Monte Carlo (DMC) simulation of p-DIB molecular crystal polymorphism. [J. Phys. Chem. Lett. 2010Lett. , 1, 1789Lett. -1794 We perform, for the first time, a rigorous study of finite-size effects and choice of nodal surface on the prediction of polymorph stability in molecular crystals using fixed-node DMC. Our calculations are the largest which are currently feasible using the resources of the K computer and provide insights into the formidable challenge of predicting such properties from first principles. In particular, we show that finite-size effects can influence the trial nodal surface of a small (1×1×1) simulation cell considerably. We therefore repeated our DMC simulations with a 1×3×3 simulation cell, which is the largest such calculation to date. We used a DFT nodal surface generated with the PBE functional and we accumulated statistical samples with ∼ 6.4 × 10 5 core-hours for each polymorph. Our final results predict a polymorph stability consistent with experiment, but indicate that results in our previous paper were somewhat fortuitous.We analyze the finite-size errors using model periodic Coulomb (MPC) interactions and kinetic energy corrections, according to the CCMH scheme of Chiesa, Ceperley, Martin, and Holzmann. We investigate the dependence of the finite-size errors on different aspect ratios of the simulation cell (k-mesh convergence) in order to understand how to choose an appropriate ratio for the DMC calculations. Even in the most expensive simulations currently possible, we show that the finite size errors in the DMC total energies are far larger than the energy difference between the two polymorphs, although error cancellation means that the polymorph prediction is accurate. Finally, we found that the T -move scheme is essential for these massive DMC simulations in order to circumvent population explosions and large time-step biases.

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Predicting Structure of Molecular Crystals from First Principles

Cited by 147 publications

References 35 publications

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Noncovalent Interactions in Organic Electronic Materials

Diffusion Monte Carlo Study of Para-Diiodobenzene Polymorphism Revisited

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