DORI Reveals the Influence of Noncovalent Interactions on Covalent Bonding Patterns in Molecular Crystals Under Pressure

Benjamin Meyer, Senja Barthel, Amber Mace, Laurent Vannay, Benoit Guillot, Berend Smit, Clémence Corminboeuf

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

The study of organic molecular crystals under high pressure provides fundamental insight into crystal packing distortions and reveals mechanisms of phase transitions and the crystallization of polymorphs. These solid-state transformations can be monitored directly by analyzing electron charge densities that are experimentally obtained at high pressure. However, restricting the analysis to the featureless electron density does not reveal the chemical bonding nature and the existence of intermolecular interactions. This shortcoming can be resolved by the use of the DORI (density overlap region indicator) descriptor, which is capable of simultaneously detecting both covalent patterns and noncovalent interactions from electron density and its derivatives. Using the biscarbonyl[14]annulene crystal under pressure as an example, we demonstrate how DORI can be exploited on experimental electron densities to reveal and monitor changes in electronic structure patterns resulting from molecular compression. A novel approach based on a flood-fill-type algorithm is proposed for analyzing the topology of the DORI isosurface. This approach avoids the arbitrary selection of DORI isovalues and provides an intuitive way to assess how compression packing affects covalent bonding in organic solids.

Original languageEnglish
Pages (from-to)1482-1488
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume10
Issue number7
DOIs
Publication statusPublished - 4 Apr 2019
Externally publishedYes

Fingerprint

Molecular crystals
Carrier concentration
Compaction
crystals
Crystals
interactions
Crystallization
Charge density
Polymorphism
Electronic structure
organic solids
Phase transitions
Topology
Derivatives
Electrons
monitors
topology
crystallization
electronic structure
solid state

Cite this

Meyer, Benjamin ; Barthel, Senja ; Mace, Amber ; Vannay, Laurent ; Guillot, Benoit ; Smit, Berend ; Corminboeuf, Clémence. / DORI Reveals the Influence of Noncovalent Interactions on Covalent Bonding Patterns in Molecular Crystals Under Pressure. In: Journal of Physical Chemistry Letters. 2019 ; Vol. 10, No. 7. pp. 1482-1488.
@article{ef39d0e71e73446295806f5b43862056,
title = "DORI Reveals the Influence of Noncovalent Interactions on Covalent Bonding Patterns in Molecular Crystals Under Pressure",
abstract = "The study of organic molecular crystals under high pressure provides fundamental insight into crystal packing distortions and reveals mechanisms of phase transitions and the crystallization of polymorphs. These solid-state transformations can be monitored directly by analyzing electron charge densities that are experimentally obtained at high pressure. However, restricting the analysis to the featureless electron density does not reveal the chemical bonding nature and the existence of intermolecular interactions. This shortcoming can be resolved by the use of the DORI (density overlap region indicator) descriptor, which is capable of simultaneously detecting both covalent patterns and noncovalent interactions from electron density and its derivatives. Using the biscarbonyl[14]annulene crystal under pressure as an example, we demonstrate how DORI can be exploited on experimental electron densities to reveal and monitor changes in electronic structure patterns resulting from molecular compression. A novel approach based on a flood-fill-type algorithm is proposed for analyzing the topology of the DORI isosurface. This approach avoids the arbitrary selection of DORI isovalues and provides an intuitive way to assess how compression packing affects covalent bonding in organic solids.",
author = "Benjamin Meyer and Senja Barthel and Amber Mace and Laurent Vannay and Benoit Guillot and Berend Smit and Cl{\'e}mence Corminboeuf",
year = "2019",
month = "4",
day = "4",
doi = "10.1021/acs.jpclett.9b00220",
language = "English",
volume = "10",
pages = "1482--1488",
journal = "Journal of Physical Chemistry Letters",
issn = "1948-7185",
publisher = "American Chemical Society",
number = "7",

}

DORI Reveals the Influence of Noncovalent Interactions on Covalent Bonding Patterns in Molecular Crystals Under Pressure. / Meyer, Benjamin; Barthel, Senja; Mace, Amber; Vannay, Laurent; Guillot, Benoit; Smit, Berend; Corminboeuf, Clémence.

In: Journal of Physical Chemistry Letters, Vol. 10, No. 7, 04.04.2019, p. 1482-1488.

Research output: Contribution to JournalArticleAcademicpeer-review

TY - JOUR

T1 - DORI Reveals the Influence of Noncovalent Interactions on Covalent Bonding Patterns in Molecular Crystals Under Pressure

AU - Meyer, Benjamin

AU - Barthel, Senja

AU - Mace, Amber

AU - Vannay, Laurent

AU - Guillot, Benoit

AU - Smit, Berend

AU - Corminboeuf, Clémence

PY - 2019/4/4

Y1 - 2019/4/4

N2 - The study of organic molecular crystals under high pressure provides fundamental insight into crystal packing distortions and reveals mechanisms of phase transitions and the crystallization of polymorphs. These solid-state transformations can be monitored directly by analyzing electron charge densities that are experimentally obtained at high pressure. However, restricting the analysis to the featureless electron density does not reveal the chemical bonding nature and the existence of intermolecular interactions. This shortcoming can be resolved by the use of the DORI (density overlap region indicator) descriptor, which is capable of simultaneously detecting both covalent patterns and noncovalent interactions from electron density and its derivatives. Using the biscarbonyl[14]annulene crystal under pressure as an example, we demonstrate how DORI can be exploited on experimental electron densities to reveal and monitor changes in electronic structure patterns resulting from molecular compression. A novel approach based on a flood-fill-type algorithm is proposed for analyzing the topology of the DORI isosurface. This approach avoids the arbitrary selection of DORI isovalues and provides an intuitive way to assess how compression packing affects covalent bonding in organic solids.

AB - The study of organic molecular crystals under high pressure provides fundamental insight into crystal packing distortions and reveals mechanisms of phase transitions and the crystallization of polymorphs. These solid-state transformations can be monitored directly by analyzing electron charge densities that are experimentally obtained at high pressure. However, restricting the analysis to the featureless electron density does not reveal the chemical bonding nature and the existence of intermolecular interactions. This shortcoming can be resolved by the use of the DORI (density overlap region indicator) descriptor, which is capable of simultaneously detecting both covalent patterns and noncovalent interactions from electron density and its derivatives. Using the biscarbonyl[14]annulene crystal under pressure as an example, we demonstrate how DORI can be exploited on experimental electron densities to reveal and monitor changes in electronic structure patterns resulting from molecular compression. A novel approach based on a flood-fill-type algorithm is proposed for analyzing the topology of the DORI isosurface. This approach avoids the arbitrary selection of DORI isovalues and provides an intuitive way to assess how compression packing affects covalent bonding in organic solids.

UR - http://www.scopus.com/inward/record.url?scp=85063131680&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85063131680&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.9b00220

DO - 10.1021/acs.jpclett.9b00220

M3 - Article

VL - 10

SP - 1482

EP - 1488

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 7

ER -