Excess electron states in fluid methane: Density-functional versus Lanczos approaches
File(s)
Accepted version
Author(s)
Saiz, F
Quirke, N
Bernasconi, L
Cubero, D
Type
Journal Article
Abstract
We compare density-functional theory (DFT) electronic structure calculations at the hybrid B3LYP level for fluid methane with experiments and a pseudo-potential Lanczos method. We generate fluid configurations from classical/ab initio molecular dynamics and use DFT to determine one-particle orbital and total energies. Our results show that DFT predicts excess electron energies that qualitatively agree with experiments over a density range, provided these values are determined from total energy differences between charged and neutral systems. By contrast, orbital energies of the lowest unoccupied state of the N-electron system provide qualitatively incorrect excess electron energies as a function of the fluid density.
Date Issued
2016-10-12
Date Acceptance
2016-10-10
Citation
Chemical Physics Letters, 2016, 664, pp.143-148
ISSN
1873-4448
Publisher
Elsevier
Start Page
143
End Page
148
Journal / Book Title
Chemical Physics Letters
Volume
664
Copyright Statement
© 2016, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/N002288/1
Subjects
02 Physical Sciences
03 Chemical Sciences
10 Technology
Publication Status
Published