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Optimized long-range corrected density functionals for electronic and optical properties of bare and ligated CdSe quantum dots

Bokareva, O. S.; Shibl, M. F.; Al-Marri, Mohammed J.; Pullerits, T. LU and Kühn, O (2017) In Journal of Chemical Theory and Computation 13(1). p.110-116
Abstract

The reliable prediction of optical and fundamental gaps of finite size systems using density functional theory requires to account for the potential self-interaction error, which is notorious for degrading the description of charge transfer transitions. One solution is provided by parametrized long-range corrected functionals such as LC-BLYP, which can be tuned such as to describe certain properties of the particular system at hand. Here, bare and 3-mercaptoprotionic acid covered Cd33Se33 quantum dots are investigated using the optimally tuned LC-BLYP functional. The range separation parameter, which determines the switching on of the exact exchange contribution, is found to be 0.12 bohr-1 and 0.09... (More)

The reliable prediction of optical and fundamental gaps of finite size systems using density functional theory requires to account for the potential self-interaction error, which is notorious for degrading the description of charge transfer transitions. One solution is provided by parametrized long-range corrected functionals such as LC-BLYP, which can be tuned such as to describe certain properties of the particular system at hand. Here, bare and 3-mercaptoprotionic acid covered Cd33Se33 quantum dots are investigated using the optimally tuned LC-BLYP functional. The range separation parameter, which determines the switching on of the exact exchange contribution, is found to be 0.12 bohr-1 and 0.09 bohr-1 for the bare and covered quantum dot, respectively. It is shown that density functional optimization indeed yields optical and fundamental gaps and thus exciton binding energies, considerably different compared with standard functionals such as the popular PBE and B3LYP ones. This holds true, despite the well established fact that the leading transitions are localized on the quantum dot and do not show pronounced long-range charge transfer character.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
13
issue
1
pages
7 pages
publisher
The American Chemical Society
external identifiers
  • scopus:85016325821
  • wos:000391898200011
ISSN
1549-9618
DOI
10.1021/acs.jctc.6b01039
language
English
LU publication?
yes
id
ac36f4d1-97dc-4e41-968e-de1339e873ed
date added to LUP
2017-04-13 11:51:15
date last changed
2018-04-15 04:42:45
@article{ac36f4d1-97dc-4e41-968e-de1339e873ed,
  abstract     = {<p>The reliable prediction of optical and fundamental gaps of finite size systems using density functional theory requires to account for the potential self-interaction error, which is notorious for degrading the description of charge transfer transitions. One solution is provided by parametrized long-range corrected functionals such as LC-BLYP, which can be tuned such as to describe certain properties of the particular system at hand. Here, bare and 3-mercaptoprotionic acid covered Cd<sub>33</sub>Se<sub>33</sub> quantum dots are investigated using the optimally tuned LC-BLYP functional. The range separation parameter, which determines the switching on of the exact exchange contribution, is found to be 0.12 bohr<sup>-1</sup> and 0.09 bohr<sup>-1</sup> for the bare and covered quantum dot, respectively. It is shown that density functional optimization indeed yields optical and fundamental gaps and thus exciton binding energies, considerably different compared with standard functionals such as the popular PBE and B3LYP ones. This holds true, despite the well established fact that the leading transitions are localized on the quantum dot and do not show pronounced long-range charge transfer character.</p>},
  author       = {Bokareva, O. S. and Shibl, M. F. and Al-Marri, Mohammed J. and Pullerits, T. and Kühn, O},
  issn         = {1549-9618},
  language     = {eng},
  number       = {1},
  pages        = {110--116},
  publisher    = {The American Chemical Society},
  series       = {Journal of Chemical Theory and Computation},
  title        = {Optimized long-range corrected density functionals for electronic and optical properties of bare and ligated CdSe quantum dots},
  url          = {http://dx.doi.org/10.1021/acs.jctc.6b01039},
  volume       = {13},
  year         = {2017},
}