Reaction pathways in the solid state and the Hubbard U correction

Trigonal rare-earth dioxymonocyanamides Ln2O2CN2 (Ln=Dy, Ho, Er, Tm, Yb) were synthesized by the modified solid-state metathesis (SSM) method, in which Ln2O3 and melamine C3N6H6 were mixed and heated at 850 °C in vacuumed silica ampoules. Possible chemical reaction pathways are proposed. X-ray diffraction (XRD) patterns of Ln2O2CN2 were refined using the Rietveld method. Compounds Ln2O2CN2 crystallize in the trigonal system with space group P3m1, Z=1, and cell parameters of a and c varying from 3.7267(1) to 3.6407(1) Å and from 8.1848(3) to 8.1152(3) Å, respectively, as Ln atoms change from Dy to Yb. These compounds have stacking structures of Ln2O22+ and CN22− layers, similar to those of previously reported compounds Ln2O2CN2 (Ln=Ce, Pr, Nd, Sm, Eu, Gd). The presence of CN22− ions has been confirmed by infrared spectroscopy, with two characteristic peaks in the vicinity of 651 and 2075 cm−1.

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A graph-based network for predicting chemical reaction pathways in solid-state materials synthesis

Nature Communications ◽

10.1038/s41467-021-23339-x ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Matthew J. McDermott ◽

Shyam S. Dwaraknath ◽

Kristin A. Persson

Keyword(s):

Solid State ◽

Chemical Reaction ◽

Reaction Pathway ◽

Reaction Network ◽

Functional Materials ◽

Reaction Pathways ◽

Materials Synthesis ◽

Pathway Prediction ◽

Solid State Materials ◽

Cost Paths

AbstractAccelerated inorganic synthesis remains a significant challenge in the search for novel, functional materials. Many of the principles which enable “synthesis by design” in synthetic organic chemistry do not exist in solid-state chemistry, despite the availability of extensive computed/experimental thermochemistry data. In this work, we present a chemical reaction network model for solid-state synthesis constructed from available thermochemistry data and devise a computationally tractable approach for suggesting likely reaction pathways via the application of pathfinding algorithms and linear combination of lowest-cost paths in the network. We demonstrate initial success of the network in predicting complex reaction pathways comparable to those reported in the literature for YMnO3, Y2Mn2O7, Fe2SiS4, and YBa2Cu3O6.5. The reaction network presents opportunities for enabling reaction pathway prediction, rapid iteration between experimental/theoretical results, and ultimately, control of the synthesis of solid-state materials.

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Mechanistic Studies of Adamantylacetophenones with Competing Reaction Pathways in Solution and in the Crystalline Solid State

The Journal of Organic Chemistry ◽

10.1021/acs.joc.9b01720 ◽

2019 ◽

Vol 84 (17) ◽

pp. 11103-11113 ◽

Cited By ~ 1

Author(s):

Vince M. Hipwell ◽

Miguel A. Garcia-Garibay

Keyword(s):

Solid State ◽

Reaction Pathways ◽

Crystalline Solid ◽

Mechanistic Studies

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Characterization of photo-intermediates in the photo-reaction pathways of a bacteriorhodopsin Y185F mutant using in situ photo-irradiation solid-state NMR spectroscopy

Photochemical & Photobiological Sciences ◽

10.1039/c5pp00154d ◽

2015 ◽

Vol 14 (9) ◽

pp. 1694-1702 ◽

Cited By ~ 7

Author(s):

Kyosuke Oshima ◽

Arisu Shigeta ◽

Yoshiteru Makino ◽

Izuru Kawamura ◽

Takashi Okitsu ◽

...

Keyword(s):

Solid State ◽

Nmr Spectroscopy ◽

Solid State Nmr ◽

Reaction Pathways ◽

Solid State Nmr Spectroscopy ◽

C Nmr

Photo-reaction pathways of a Y185F-bR mutant and, CS*- and O-intermediates were examined using in situ photo-irradiation solid-state 13C NMR spectroscopy.

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Solid-state reaction pathways of Sillenite-phase formation studied by high-temperature X-ray diffractometry and differential thermal analysis

Materials Research Bulletin ◽

10.1016/s0025-5408(03)00025-4 ◽

2003 ◽

Vol 38 (5) ◽

pp. 875-897 ◽

Cited By ~ 29

Author(s):

Sam Chehab ◽

Pierre Conflant ◽

Michel Drache ◽

Jean-Claude Boivin ◽

George McDonald

Keyword(s):

Thermal Analysis ◽

Differential Thermal Analysis ◽

High Temperature ◽

Solid State ◽

Phase Formation ◽

Solid State Reaction ◽

Reaction Pathways ◽

X Ray

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Reaction Pathways in Solid-State Processes. 1. Carbon-13 NMR and X-ray Crystallography of Fluorobullvalene

Journal of the American Chemical Society ◽

10.1021/ja954005l ◽

1996 ◽

Vol 118 (34) ◽

pp. 8006-8014 ◽

Cited By ~ 11

Author(s):

K. Müller ◽

H. Zimmermann ◽

C. Krieger ◽

R. Poupko ◽

Z. Luz

Keyword(s):

Solid State ◽

Reaction Pathways ◽

X Ray ◽

X Ray Crystallography

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Combining Quantum Mechanical Reaction Pathways with Force Field Lattice Interactions To Model a Solid-State Phototransformation

Journal of the American Chemical Society ◽

10.1021/ja962734a ◽

1997 ◽

Vol 119 (6) ◽

pp. 1474-1475 ◽

Cited By ~ 14

Author(s):

Amy E. Keating ◽

Steve H. Shin ◽

K. N. Houk ◽

Miguel A. Garcia-Garibay

Keyword(s):

Solid State ◽

Force Field ◽

Reaction Pathways ◽

Quantum Mechanical

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A graph-based network for predicting chemical reaction pathways in solid-state materials synthesis

10.21203/rs.3.rs-38000/v1 ◽

2020 ◽

Author(s):

Matthew J. McDermott ◽

Shyam S. Dwaraknath ◽

Kristin A. Persson

Keyword(s):

Solid State ◽

Chemical Reaction ◽

Reaction Pathway ◽

Reaction Network ◽

Functional Materials ◽

Inorganic Materials ◽

Reaction Pathways ◽

Materials Synthesis ◽

Solid State Materials ◽

Cost Paths

Abstract Accelerated synthesis of inorganic materials remains a significant challenge in the search for novel, functional materials. Many of the chemical principles which enable "synthesis by design" in synthetic organic chemistry do not exist in solid-state chemistry, despite extensive computed/experimental thermochemistry data. We present a chemical reaction network model constructed from thermochemistry databases that captures features of the thermodynamic phase space which synthesis reactions traverse. Directed edges in the network are assigned weights via a transformation that maps reaction parameters to costs. We devise a computationally tractable approach for suggesting likely reaction pathways via application of pathfinding algorithms and linear combination of lowest-cost paths in the network. We demonstrate initial success of the reaction network in predicting a complex metathesis reaction pathway toward yttrium manganese oxide YMnO3. The reaction network presents new opportunities for enabling reaction pathway prediction, rapid iteration between experimental/theoretical results, and ultimately, control of synthesis of solid-state materials.

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