Anisotropic thermal motion in transition-metal carbonyls from experiments and ab initio theory

Deringer, Volker L.; Wang, Ai; George, Janine; Dronskowski, Richard; Englert, Ulli

doi:10.1039/c6dt02487d

Cited by 16 publications

(28 citation statements)

References 62 publications

(38 reference statements)

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“…Table S2. Atomic coordinates for bromomalonic aldehyde X y z Br (1) .5000 .40465 (2) .54829(3) O (1) .5000 .14233 (12) .77538(17) O (2) .5000 .30282 (11) .08673(16) C (1) .5000 .13756 (13) .58267(18) C (2) .5000 .24171 (11) .44204(17) C (3) .5000 .21702 (12) .23386(18) H (2) .5000 .2678 −.0309 H (1) .5000 .0570 .5212 H (3) .5000 .1322 .1914 Table S3. Bond lengths (in Å) and angles (°) for bromomalonic aldehyde Br(1)−C(2) 1.8759 (12) Table S4.…”

Section: Supplementary Materialsmentioning

confidence: 99%

Lattice thermal expansion and anisotropic displacements in urea, bromomalonic aldehyde, pentachloropyridine, and naphthalene

George

Wang

Englert

et al. 2017

The Journal of Chemical Physics

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Anisotropic displacement parameters (ADPs) are commonly used in crystallography, chemistry, and related fields to describe and quantify thermal motion of atoms. Within the very recent years, these ADPs have become predictable by lattice dynamics in combination with first-principles theory. Here, we study four very different molecular crystals, namely, urea, bromomalonic aldehyde, pentachloropyridine, and naphthalene, by first-principles theory to assess the quality of ADPs calculated in the quasi-harmonic approximation. In addition, we predict both the thermal expansion and thermal motion within the quasi-harmonic approximation and compare the predictions with the experimental data. Very reliable ADPs are calculated within the quasi-harmonic approximation for all four cases up to at least 200 K, and they turn out to be in better agreement with the experiment than those calculated within the harmonic approximation. In one particular case, ADPs can even reliably be predicted up to room temperature. Our results also hint at the importance of normal-mode anharmonicity in the calculation of ADPs.

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Section: Supplementary Materialsmentioning

confidence: 99%

Lattice thermal expansion and anisotropic displacements in urea, bromomalonic aldehyde, pentachloropyridine, and naphthalene

George

Wang

Englert

et al. 2017

The Journal of Chemical Physics

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“…This method is commonly used in current work on ADP prediction. 13,16,[18][19][20] We have gathered experimental benchmark values at 100, 150, and 200 K using single-crystal XRD, and use these to assess our computed values at the different levels of theory (Fig. 4a).…”

Section: B Adps In the Harmonic Approximationmentioning

confidence: 99%

Lattice thermal expansion and anisotropic displacements in 𝜶-sulfur from diffraction experiments and first-principles theory

George

Deringer

Wang

et al. 2016

The Journal of Chemical Physics

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Thermal properties of solid-state materials are a fundamental topic of study with important practical implications. For example, anisotropic displacement parameters (ADPs) are routinely used in physics, chemistry, and crystallography to quantify the thermal motion of atoms in crystals. ADPs are commonly derived from diffraction experiments, but recent developments have also enabled their first-principles prediction using periodic density-functional theory (DFT). Here, we combine experiments and dispersion-corrected DFT to quantify lattice thermal expansion and ADPs in crystalline α-sulfur (S), a prototypical elemental solid that is controlled by the interplay of covalent and van der Waals interactions. We begin by reporting on single-crystal and powder X-ray diffraction measurements that provide new and improved reference data from 10 K up to room temperature. We then use several popular dispersion-corrected DFT methods to predict vibrational and thermal properties of α-sulfur, including the anisotropic lattice thermal expansion. Hereafter, ADPs are derived in the commonly used harmonic approximation (in the computed zero-Kelvin structure) and also in the quasi-harmonic approximation (QHA) which takes the predicted lattice thermal expansion into account. At the PPBE+D3(BJ) level, the QHA leads to excellent agreement with experiments. Finally, more general implications of this study for theory and experiment are discussed.

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“…Lattice parameters of the minimum energy structures match those observed experimentally equally well for 1 and 2, but a different picture is obtained when displacement parameters are considered. At low temperatures, such as 100 or 150 K, theoretical ADPs from first principles based on the harmonic approximation can be expected to match experiments reasonably well (George et al, 2015a,b;Deringer et al, 2016;Mroz et al, 2019). Fig.…”

Section: Resultsmentioning

confidence: 87%

“…This progress has been benchmarked by comparison with the results from single-crystal X-ray or neutron diffraction. In this context, a 'heavy atom problem' with ADPs from theory was suspected (Deringer et al, 2016) but not conclusively proven. We therefore decided to calculate the ADPs in two isomorphous (Authier & Chapuis, 2014; IUCr Online Dictionary of Crystallography, 2017) organic crystals and compare the results from theory to their experimental counterparts.…”

Section: Introductionmentioning

confidence: 99%

Can we trust the experiment? Anisotropic displacement parameters in 1-(halomethyl)-3-nitrobenzene (halogen = Cl or Br)

Mroz¹,

Wang²,

Englert³

et al. 2020

Acta Crystallogr C

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1‐(Chloromethyl)‐3‐nitrobenzene, C7H6NClO2, and 1‐(bromomethyl)‐3‐nitrobenzene, C7H6NBrO2, were chosen as test compounds for benchmarking anisotropic displacement parameters (ADPs) calculated from first principles in the harmonic approximation. Crystals of these compounds are isomorphous, and theory predicted similar ADPs for both. In‐house diffraction experiments with Mo Kα radiation were in apparent contradiction to this theoretical result, with experimentally observed ADPs significantly larger for the bromo derivative. In contrast, the experimental and theoretical ADPs for the lighter congener matched reasonably well. As all usual quality indicators for both sets of experimental data were satisfactory, complementary diffraction experiments were performed at a synchrotron beamline with shorter wavelength. Refinements based on these intensity data gave very similar ADPs for both compounds and were thus in agreement with the earlier in‐house results for the chloro derivative and the predictions of theory. We speculate that strong absorption by the heavy halogen may be the reason for the observed discrepancy.

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Anisotropic thermal motion in transition-metal carbonyls from experiments and ab initio theory

Cited by 16 publications

References 62 publications

Lattice thermal expansion and anisotropic displacements in urea, bromomalonic aldehyde, pentachloropyridine, and naphthalene

Lattice thermal expansion and anisotropic displacements in urea, bromomalonic aldehyde, pentachloropyridine, and naphthalene

Lattice thermal expansion and anisotropic displacements in 𝜶-sulfur from diffraction experiments and first-principles theory

Can we trust the experiment? Anisotropic displacement parameters in 1-(halomethyl)-3-nitrobenzene (halogen = Cl or Br)

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