Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

Simple item page
dc.citation.journalTitleThe Journal of Physical Chemistry A
dc.contributor.authorGarza, Alejandro J.
dc.contributor.authorWazzan, Nuha A.
dc.contributor.authorAsiri, Abdullah M.
dc.contributor.authorScuseria, Gustavo E.
dc.date.accessioned2014-12-10T15:47:11Z
dc.date.available2014-12-10T15:47:11Z
dc.date.issued2014
dc.description.abstractThe hyperpolarizabilities of five prototypical and four recently synthesized long-range charge-transfer (CT) organic compounds are calculated using short- and middle-range (SR and MR) hybrid functionals. These results are compared with data from MP2 and other DFT methods including GGAs, global hybrids, long-range corrected functionals (LC-DFT), and optimally tuned LC-DFT. Although it is commonly believed that the overestimation of hyperpolarizabilities associated with CT excitations by GGA and global hybrid functionals is the result of their wrong asymptotic exchange potential, and that LC-DFT heals this issue, we show here that SR and MR functionals yield results similar to those from LC-DFT. Hence, the long-range correction per se does not appear to be the key element in the well-known improved description of hyperpolarizabilities by LC-DFT. Rather, we argue that the inclusion of substantial amounts of Hartree-Fock exchange, which reduces the many-electron self-interaction error, is responsible for the relatively good results afforded by range separated hybrids. Additionally, we evaluate the effects of solvent and frequency on hyperpolarizabilities computed by SR and MR hybrids and compare these predictions with other DFT methods and available experimental data.
dc.identifier.citationGarza, Alejandro J., Wazzan, Nuha A., Asiri, Abdullah M., et al.. "Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?." <i>The Journal of Physical Chemistry A,</i> (2014) American Chemical Society: http://dx.doi.org/10.1021/jp510062b.
dc.identifier.doihttp://dx.doi.org/10.1021/jp510062b
dc.identifier.urihttps://hdl.handle.net/1911/78734
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.rightsThis is an author's peer-reviewed final manuscript, as accepted by the publisher. The published article is copyrighted by the American Chemical Society.
dc.subject.keywordDFT
dc.subject.keywordrange separated hybrids
dc.subject.keywordoptimal tuning
dc.subject.keywordself-interaction error
dc.subject.keywordorganic materials
dc.subject.keywordnonlinear optics
dc.titleCan Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?
dc.typeJournal article
dc.type.dcmiText
dc.type.publicationpost-print
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
main.pdf
Size:
3.83 MB
Format:
Adobe Portable Document Format
Description:
Download
Collections
Faculty Publications
Chemistry Publications
Physics and Astronomy Publications