Issue 20, 2017

Thermodynamic cycles of the alkali metal–ligand complexes central to electride formation

Abstract

Alkali metal–ligand complexes are the building blocks of the exotic organic alkalide and electride materials. In this work, density-functional theory is used to construct thermodynamic cycles for the alkali metal–ligand complexes, highlighting the energy changes that enable alkalide and electride formation. Strong alkali metal- and cation-to-ligand binding energies are predicted and Rydberg-like ground states of the alkali metal–ligand complexes are identified, consistent with previous work. Calculations on molecular electride species do not reveal consistency with the identified trends, suggesting that the molecular electrides are a class of material unto themselves. The ionisation potentials of the alkali metal–ligand complexes are calculated to be consistently between 1 and 2 eV, suggesting that a specific ionisation potential (IP) is central to electride formation. Further, the thermodynamic cycle for the simplest electride, Cs+(15C5)2e, shows stabilisation of the solid crystal due to electride formation that is consistent in magnitude with the IP of the equivalent alkali metal–ligand complex. In light of this, computational screening of the alkali metal–ligand complexes' IP presents a new design criterion for alkalide and electride materials.

Graphical abstract: Thermodynamic cycles of the alkali metal–ligand complexes central to electride formation

Supplementary files

Article information

Article type
Paper
Submitted
09 2 2017
Accepted
18 4 2017
First published
25 4 2017

Phys. Chem. Chem. Phys., 2017,19, 12816-12825

Thermodynamic cycles of the alkali metal–ligand complexes central to electride formation

S. G. Dale and E. R. Johnson, Phys. Chem. Chem. Phys., 2017, 19, 12816 DOI: 10.1039/C7CP00882A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements