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A first principles study on the dissociation and rotation processes of a single O2 molecule on the Pt(111) surface
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).ORCID iD: 0000-0003-0007-0394
2011 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 14, 6864-6869 p.Article in journal (Refereed) Published
Abstract [en]

Through density functional theory calculations, a detailed description on the dissociation and rotation processes of a single oxygen molecule adsorbed on the Pt(111) surface has been provided. Both dissociation and rotation reaction pathways have been identified, and some interesting phenomena related to the scanning tunneling microscopy experiments are finally explained. It is found that the prior occupation of oxygen atom on the metastable hcp-hollow site after O2 dissociation is originated from the particular structure of the intermediate state, and the low energy barrier of the O2 rotation can be attributed to an effective pathway. The experimentally observed noninteger power-law dependence of the rotation rate as a function of the current has been accurately determined by a newly developed statistical model for the inelastic electron tunneling. By considering the randomness of multielectron inelastic tunneling processes, it is found that the noninteger exponent comes from a statistical contribution of various n-electron events.

Place, publisher, year, edition, pages
American Chemical Society , 2011. Vol. 115, no 14, 6864-6869 p.
Keyword [en]
scanning tunneling microscope, density-functional theory, total-energy calculations, wave basis-set, atom-transfer, oxygen dissociation, adsorption, mechanism, switch, spectroscopy
National Category
Theoretical Chemistry
URN: urn:nbn:se:kth:diva-33362DOI: 10.1021/jp200687tISI: 000289215400090ScopusID: 2-s2.0-79953766611OAI: diva2:414680
Swedish Research Council
Available from: 2011-05-04 Created: 2011-05-04 Last updated: 2011-09-08Bibliographically approved
In thesis
1. Understanding the Structure and Reaction of Single Molecules on Metal surfaces from First Principles
Open this publication in new window or tab >>Understanding the Structure and Reaction of Single Molecules on Metal surfaces from First Principles
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The study of surface adsorption and reaction is not only interesting from a scientific point of view, but also important in many application fields such as energy, environment, catalysis, corrosion, electronic device, and sensor. Theoretical calculations are essential in these studies.

In this thesis, first principles studies for the structure and reaction of some important single molecules on the surface are presented. Dehydrogenation of single trans-2-butene molecule on a Pd(110) surface is the first example. The adsorption configurations of both reactant and produce are assigned and the whole dehydrogenation pathway is revealed. Our calculations show that the reactant, i.e. trans-2-butene molecule, undergoes a rotation before dehydrogenation occurs, which is an important detail that cannot be observed directly in scanning tunneling microscopy (STM) experiments. The dissociation and rotation processes of single oxygen molecule on a Pt(111) surface have been a subject of extensive studies in the past. A new intermediate state with a peculiar configuration is identified. The puzzled adsorption site is well explained. The calculated energy barriers agree well with experimental results for both dissociation and rotation processes.

Another aspect addressed in this thesis is the mechanism of molecular electronic switches induced by molecular structural changes. By carefully examining the tautomerization process of a naphthalocyanine molecule, an intermediate state is located on the potential surface of the tautomerization. Our calculations indicate that the experimentally observed switching involves four-states, rather than the two-state as proposed by the experimentalists. In a joint experimental and theoretical study the dehydrogenation, tautomerization, and mechanical switching processes of a single melamine molecule on a Cu(100) surface have been comprehensively examined. A new dual-functional molecular device with integrated rectifying and switching functions is made for the first time. In collaborating with another experimental group, we have simulated the switching process of a single 1,1,2,3,4,5-hexaphenylsilole molecule on a Cu(111) surface. The role of the orientation of the molecule is carefully examined and a new switching mechanism is proposed.

Switching processes are strongly associated with the inelastic electron tunneling. We have proposed a statistical model that allows explaining the non-integer exponent in the power-law relationship between the switching rate and tunneling current. In this model, the importance of the randomness in inelastic electron excitations and the lifetime of the immediate state are emphasized. It has shown that the inelastic electron tunneling is a collection of various n-electron processes with different statistical weight.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. xii, 72 p.
Trita-BIO-Report, ISSN 1654-2312 ; 2011:16
National Category
Theoretical Chemistry
urn:nbn:se:kth:diva-33565 (URN)978-91-7415-978-3 (ISBN)
Public defence
2011-06-10, FA32, AlbaNova University Center, Roslagstullsbacken 21, Stockholm, 10:00 (English)
QC 20110524Available from: 2011-05-24 Created: 2011-05-10 Last updated: 2011-05-24Bibliographically approved

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