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The equilibrium geometry of A@C60: A test case for conventional density functional theory
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
North China Electric Power University, Beijing, China.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
Shandong Normal University.
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2014 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 591, 312-316 p.Article in journal (Refereed) Published
Abstract [en]

Potential energy surfaces (PESs) along the reaction pathway towards the center of CC bond between two six membered rings for ten different endohedral fullerenes A@C60 (A = H, C, O, S, N, P, He, Ne, Ar, Kr) have been studied by density functional theory (DFT) and Hartree-Fock (HF) method. The results show that no suitable method can consistently describe the interaction between atom A and carbon cage. The dispersion corrected DFT methods fail to describe the equilibrium geometry and PES of the complexes with light atoms. Nevertheless, the inclusion of the dispersion stabilizes the system as reflected by interaction energies (IEs) between atom A and C60.

Place, publisher, year, edition, pages
2014. Vol. 591, 312-316 p.
Keyword [en]
Carbon cages, Endohedral fullerene, Equilibrium geometries, Hartree-Fock methods, Interaction energies, Light atoms, Reaction pathways, Six-membered rings
National Category
Theoretical Chemistry
URN: urn:nbn:se:kth:diva-95373DOI: 10.1016/j.cplett.2013.11.050ISI: 000329210200063ScopusID: 2-s2.0-84890827107OAI: diva2:527966

QC 20140204. Updated from submitted to published. Previous title: "The equilibrium geometry of A@C60: a difficult case for conventional dentisy functional theory"

Available from: 2012-05-23 Created: 2012-05-23 Last updated: 2014-02-11Bibliographically approved
In thesis
1. Theoretical Characterization of Functional Molecular Materials
Open this publication in new window or tab >>Theoretical Characterization of Functional Molecular Materials
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nowadays, material, energy and information technologies are three pillar industries. The materials that have close relation with our life have also been the foundation for the development of energy and information technologies. As the new member of the material family, functional molecular materials have become increasingly important for many applications, for which the design and characterization by the theoretical modeling have played the vital role. In this thesis, three different categories of functional molecular materials, the endohedral fullerenes, the fullerene derivatives and the self-assembled monolayers (SAMs), have been studied by means of first principles methods.

The non-metal endohedral fullerene N@C60 is a special endohedral fullerene that is believed to be relevant to the construction of future quantum computer. The energy landscape inside the N@C60 has been carefully explored by density functional theory (DFT) calculations. The most energy favorable potential energysurfaces (PESs) for the N atom to move within the cavity have been identified. The effect of the charging on the PESs has also been examined. It is found that the inclusion of dispersion force is essential in determining the equilibriumstructure of N@C60. Furthermore, the performance of several commonly useddensity functionals with or without dispersion correction has been verified for ten different endohedral fullerenes A@C60 with the atom A being either reactive nonmetal or nobel gases elements. It shows that the inclusion of the dispersion forcedoes provide better description for the binding energy (BE), however, none ofthem could correctly describe the energy landscape inside all the ten endohedral fullerenes exclusively. It thus calls for the further improvement of current density functionals for weak interacting systems.

Soft X-ray spectroscopy is a powerful tool for studying the chemical and electronic structures of functional molecular materials. Theoretical calculations have been proven to be extremely useful for providing correct assignments for spectraof large systems. In this thesis, we have performed first principles simulations forthe near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectra (XPS) of fullerene derivatives and aminothiolates SAMs. Our calculatedspectra can accurately reproduce experimental results available for all the systemsunder investigations, and identify the species or structures that are responsible for those unexpected spectral features observed in experiments. We have suggested a modified building block (MBB) approach that allows to calculate NEXAFS spectraof a large number of fullerene derivatives with very small computational cost, and resolved the long standing puzzle around the experimental XPS and NEXAFS spectra of SAMs with aminothiolates.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. xviii, 49 p.
TRITA-BIO-Report, ISSN 1654-2312 ; 2012:16
first-principles, soft X-ray spectroscopy, endohedral fullerene, fullerene derivatives, self-assembled monolayers
National Category
Theoretical Chemistry
Research subject
SRA - Molecular Bioscience
urn:nbn:se:kth:diva-94540 (URN)978-91-7501-367-1 (ISBN)
Public defence
2012-06-08, FD5, AlbaNova University Center, Roslagstullsbacken 21, Stockholm, 10:00 (English)

QC 20120523

Available from: 2012-05-23 Created: 2012-05-09 Last updated: 2014-02-04Bibliographically approved

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