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Brinck, T. & Nyberg Borrfors, A. (2019). Electrostatics and polarization determine the strength of the halogen bond: a red card for charge transfer. JOURNAL OF MOLECULAR MODELING, 25(5), Article ID 125.
Open this publication in new window or tab >>Electrostatics and polarization determine the strength of the halogen bond: a red card for charge transfer
2019 (English)In: JOURNAL OF MOLECULAR MODELING, Vol. 25, no 5, article id 125Article in journal (Refereed) Published
Abstract [en]

A series of 20 halogen bonded complexes of the types R-Br center dot center dot center dot Br- (R is a substituted methyl group) and R '-CC-Br center dot center dot center dot Br- are investigated at the M06-2X/6-311+G(d,p) level of theory. Computations using a point-charge (PC) model, in which Br- is represented by a point charge in the electronic Hamiltonian, show that the halogen bond energy within this set of complexes is completely described by the interaction energy (E-PC) of the point charge. This is demonstrated by an excellent linear correlation between the quantum chemical interaction energy and E-PC with a slope of 0.88, a zero intercept, and a correlation coefficient of R-2=0.9995. Rigorous separation of E-PC into electrostatics and polarization shows the high importance of polarization for the strength of the halogen bond. Within the data set, the electrostatic interaction energy varies between 4 and-18kcal mol(-1), whereas the polarization energy varies between -4 and-10kcal mol(-1). The electrostatic interaction energy is correlated to the sum of the electron-withdrawing capacities of the substituents. The polarization energy generally decreases with increasing polarizability of the substituents, and polarization is mediated by the covalent bonds. The lower (more favorable) E-PC of CBr4---Br- compared to CF3Br center dot center dot center dot Br- is found to be determined by polarization as the electrostatic contribution is more favorable for CF3Br center dot center dot center dot Br-. The results of this study demonstrate that the halogen bond can be described accurately by electrostatics and polarization without any need to consider charge transfer.

Place, publisher, year, edition, pages
SPRINGER, 2019
Keywords
Halogen bonding, Electrostatic potential, Induction, Charge transfer, Energy decomposition, Sigma-hole
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-251273 (URN)10.1007/s00894-019-4014-7 (DOI)000465614200004 ()31020416 (PubMedID)2-s2.0-85064683551 (Scopus ID)
Note

QC 20190514

Available from: 2019-05-14 Created: 2019-05-14 Last updated: 2019-05-29Bibliographically approved
Brinck, T. & Stenlid, J. H. (2019). The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science. ADVANCED THEORY AND SIMULATIONS, 2(1), Article ID 1800149.
Open this publication in new window or tab >>The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science
2019 (English)In: ADVANCED THEORY AND SIMULATIONS, ISSN 2513-0390, Vol. 2, no 1, article id 1800149Article in journal (Refereed) Published
Abstract [en]

The current status of the molecular surface property approach (MSPA) and its application for analysis and prediction of intermolecular interactions, including chemical reactivity, are reviewed. The MSPA allows for identification and characterization of all potential interaction sites of a molecule or nanoparticle by the computation of one or more molecular properties on an electronic isodensity surface. A wide range of interactions can be analyzed by three properties, which are well-defined within Kohn-Sham density functional theory. These are the electrostatic potential, the average local ionization energy, and the local electron attachment energy. The latter two do not only reflect the electrostatic contribution to a chemical interaction, but also the contributions from polarization and charge transfer. It is demonstrated that the MSPA has a high predictive capacity for non-covalent interactions, for example, hydrogen and halogen bonding, as well as organic substitution and addition reactions. The latter results open u p applications within drug design and medicinal chemistry. The application of MSPA has recently been extended to nanoparticles and extended surfaces of metals and metal oxides. In particular, nanostructural effects on the catalytic properties of noble metals are rationalized. The potential for using MSPA in rational design of heterogeneous catalysts is discussed.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2019
Keywords
average local ionization energy, electrostatic potential, heterogeneous catalysis, local electron attachment energy, regium bonding
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-242182 (URN)10.1002/adts.201800149 (DOI)000455107500016 ()
Note

QC 20190128

Available from: 2019-01-28 Created: 2019-01-28 Last updated: 2019-04-29Bibliographically approved
Tissot, H., Wang, C., Sterdid, J. H., Brinck, T. & Weissenrieder, J. (2019). The Surface Structure of Cu2O(100): Nature of Defects. The Journal of Physical Chemistry C, 123(13), 7696-7704
Open this publication in new window or tab >>The Surface Structure of Cu2O(100): Nature of Defects
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2019 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 123, no 13, p. 7696-7704Article in journal (Refereed) Published
Abstract [en]

The Cu2O(100) surface is most favorably terminated by a (3,0;1,1) reconstruction under ultrahigh-vacuum conditions. As most oxide surfaces, it exhibit defects, and it is these sites that are focus of attention in this study. The surface defects are identified, their properties are investigated, and procedures to accurately control their coverage are demonstrated by a combination of scanning tunneling microscopy (STM) and simulations within the framework of density functional theory (DFT). The most prevalent surface defect was identified as an oxygen vacancy. By comparison of experimental results, formation energies, and simulated STM images, the location of the oxygen vacancies was identified as an oxygen vacancy in position B, located in the valley between the two rows of oxygen atoms terminating the unperturbed surface. The coverage of defects is influenced by the surface preparation parameters and the history of the sample. Furthermore, using low-energy electron beam bombardment, we show that the oxygen vacancy coverage can be accurately controlled and reach a complete surface coverage (1 per unit cell or 1.8 defects per nm(2)) without modification to the periodicity of the surface, highlighting the importance of using local probes when investigating oxide surfaces.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Other Materials Engineering
Identifiers
urn:nbn:se:kth:diva-251204 (URN)10.1021/acs.jpcc.8b05156 (DOI)000463844500019 ()2-s2.0-85050489968 (Scopus ID)
Note

QC 20190724

Available from: 2019-07-24 Created: 2019-07-24 Last updated: 2019-07-24Bibliographically approved
Liljenberg, M., Halldin Stenlid, J. & Brinck, T. (2018). Mechanism and regioselectivity of electrophilic aromatic nitration in solution: the validity of the transition state approach. Journal of Molecular Modeling, 24(1), Article ID 15.
Open this publication in new window or tab >>Mechanism and regioselectivity of electrophilic aromatic nitration in solution: the validity of the transition state approach
2018 (English)In: Journal of Molecular Modeling, ISSN 1610-2940, E-ISSN 0948-5023, Vol. 24, no 1, article id 15Article in journal (Refereed) Published
Abstract [en]

The potential energy surfaces in gas phase and in aqueous solution for the nitration of benzene, chlorobenzene, and phenol have been elucidated with density functional theory at theM06-2X/6-311G(d,p) level combined with the polarizable continuum solvent model (PCM). Three reaction intermediates have been identified along both surfaces: the unoriented pi-complex (I), the oriented reaction complex (II), and the sigma-complex (III). In order to obtain quantitatively reliable results for positional selectivity and for modeling the expulsion of the proton, it is crucial to take solvent effects into consideration. The results are in agreement with Olah's conclusion from over 40 years ago that the transition state leading to (II) is the rate-determining step in activated cases, while it is the one leading to (III) for deactivated cases. The simplified reactivity approach of using the free energy for the formation of (III) as a model of the rate-determining transition state has previously been shown to be very successful for halogenations, but problematic for nitrations. These observations are rationalized with the geometric and energetic resemblance, and lack of resemblance respectively, between (III) and the corresponding rate determining transition state. At this level of theory, neither the sigma-complex (III) nor the reaction complex (II) can be used to accurately model the rate-determining transition state for nitrations.

Place, publisher, year, edition, pages
SPRINGER, 2018
Keywords
Nitration, Electrophilic aromatic substitution, Transition state, Regioselectivity, Quantumchemistry
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-222199 (URN)10.1007/s00894-017-3561-z (DOI)000422667900038 ()2-s2.0-85038842979 (Scopus ID)
Note

QC 20180205

Available from: 2018-02-05 Created: 2018-02-05 Last updated: 2018-03-13Bibliographically approved
Liljenberg, M., Halldin Stenlid, J. & Brinck, T. (2018). Theoretical Investigation into Rate-Determining Factors in Electrophilic Aromatic Halogenation. Journal of Physical Chemistry A, 122(12), 3270-3279
Open this publication in new window or tab >>Theoretical Investigation into Rate-Determining Factors in Electrophilic Aromatic Halogenation
2018 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 12, p. 3270-3279Article in journal (Refereed) Published
Abstract [en]

The halogenation of monosubstituted benzenes in aqueous solvent was studied using density functional theory at the PCM-M06-2X/6-311G(d,p) level. The reaction with Cl-2 begins with the formation of C atom coordinated pi-complex and is followed by the formation of the sigma-complex, which is rate-determining. The final part proceeds via the abstraction of the proton by a water molecule or a weak base. We evaluated the use of the sigma-complex as a model for the rate-determining transition state (TS) and found that this model is more accurate the later the TS comes along the reaction coordinate. This explains the higher accuracy of the model for halogenations (late TS) compared to nitrations (early TS); that is, the more deactivated the substrate the later the TS. The halogenation with Br-2 proceeds with a similar mechanism as the corresponding chlorination, but the bromination has a very late rate-determining TS that is similar to the sigma-complex in energy. The iodination with ICl follows a different mechanism than chlorination and bromination. After the formation of the pi-complex, the reaction proceeds in a concerted manner without a sigma-complex. This reaction has a large primary hydrogen kinetic isotope effect in agreement with experimental observations.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-226789 (URN)10.1021/acs.jpca.7b10781 (DOI)000429080300020 ()29505259 (PubMedID)2-s2.0-85044836973 (Scopus ID)
Note

QC 20180504

Available from: 2018-05-04 Created: 2018-05-04 Last updated: 2018-06-04Bibliographically approved
Halldin Stenlid, J., Johansson, A. J., Leygraf, C. & Brinck, T. (2017). Atomic-scale modelling of copper corrosion in anoxic and sulphide containing water. In: EUROCORR 2017 - The Annual Congress of the European Federation of Corrosion, 20th International Corrosion Congress and Process Safety Congress 2017: . Paper presented at Joint European Corrosion Congress 2017, EUROCORR 2017 and 20th International Corrosion Congress and Process Safety Congress 2017. Asociace koroznich inzenyru z.s.- AKI - Czech Association of Corrosion Engineers
Open this publication in new window or tab >>Atomic-scale modelling of copper corrosion in anoxic and sulphide containing water
2017 (English)In: EUROCORR 2017 - The Annual Congress of the European Federation of Corrosion, 20th International Corrosion Congress and Process Safety Congress 2017, Asociace koroznich inzenyru z.s.- AKI - Czech Association of Corrosion Engineers , 2017Conference paper, Published paper (Refereed)
Place, publisher, year, edition, pages
Asociace koroznich inzenyru z.s.- AKI - Czech Association of Corrosion Engineers, 2017
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-234517 (URN)2-s2.0-85052295357 (Scopus ID)
Conference
Joint European Corrosion Congress 2017, EUROCORR 2017 and 20th International Corrosion Congress and Process Safety Congress 2017
Note

QC 20180907

Available from: 2018-09-07 Created: 2018-09-07 Last updated: 2018-09-07Bibliographically approved
Halldin Stenlid, J., Johansson, A. J., Leygraf, C. & Brinck, T. (2017). Computational Analysis of the Early Stage of Cuprous Oxide Sulphidation: A Top-Down Process. Corrosion Engineering, Science and Technology, 52(S1), 50-53
Open this publication in new window or tab >>Computational Analysis of the Early Stage of Cuprous Oxide Sulphidation: A Top-Down Process
2017 (English)In: Corrosion Engineering, Science and Technology, ISSN 1478-422X, E-ISSN 1743-2782, Vol. 52, no S1, p. 50-53Article in journal (Refereed) Published
Abstract [en]

The initial steps of Cu2O sulphidation to Cu2S have been studied using plane-wave density functional theory at the PBE-D3+U level of sophistication. Surface adsorption and dissociation of H2S and H2O, as well as the replacement reaction of lattice oxygen with sulphur, have been investigated for the most stable (111) and (100) surface facets under oxygen-lean conditions. We find that the (100) surface is more susceptible to sulphidation than the (111) surface, promoting both H2S adsorption, dissociation and the continued oxygen–sulphur replacement. The results presented in this proceeding bridge previous results from high-vacuum experiments on ideal surface to more realistic corrosion conditions and set the grounds for future mechanistic studies. Potential implications on the long-term final disposal of spent nuclear fuel are discussed.

Keywords
Density functional theory, sulphidation, cuprite (Cu2O), corrosion, water (H2O), hydrogen sulphide (H2S), nuclear waste disposal, chalcocite (Cu2S)
National Category
Chemical Sciences
Research subject
Materials Science and Engineering; Chemistry; Theoretical Chemistry and Biology
Identifiers
urn:nbn:se:kth:diva-212933 (URN)10.1080/1478422X.2017.1284393 (DOI)
Note

QC 20170829

Available from: 2017-08-24 Created: 2017-08-24 Last updated: 2017-08-29Bibliographically approved
Besharat, Z., Halldin Stenlid, J., Soldemo, M., Marks, K., Önsten, A., Johnson, M., . . . Göthelid, M. (2017). Dehydrogenation of methanol on Cu2O(100) and (111). Journal of Chemical Physics, 146(24)
Open this publication in new window or tab >>Dehydrogenation of methanol on Cu2O(100) and (111)
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2017 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 146, no 24Article in journal (Refereed) Published
Abstract [en]

Adsorption and desorption of methanol on the (111) and (100) surfaces of  Cu2O have been studied using high-resolution photoelectron spectroscopy in the temperature range 120–620 K, in combination with density functional theorycalculations and sum frequency generation spectroscopy. The bare (100) surfaceexhibits a (3,0; 1,1) reconstruction but restructures during the adsorption process into a Cu-dimer geometry stabilized by methoxy and hydrogen binding in Cu-bridge sites. During the restructuring process, oxygen atoms from the bulk that can host hydrogen appear on the surface. Heating transforms methoxy to formaldehyde, but further dehydrogenation is limited by the stability of the surface and the limited access to surface oxygen. The (√3 × √3)R30°-reconstructed (111) surface is based on ordered surface oxygen and copper ions and vacancies, which offers a palette of adsorption and reaction sites. Already at 140 K, a mixed layer of methoxy, formaldehyde, and CHxOy is formed. Heating to room temperature leaves OCH and CHx. Thus both CH-bond breaking and CO-scission are active on this  surface at low temperature. The higher ability to dehydrogenate methanol on (111) compared to (100) is explained by the multitude of adsorption sites and, in particular, the availability of surfaceoxygen.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2017
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-211786 (URN)10.1063/1.4989472 (DOI)000404302600033 ()2-s2.0-85021446807 (Scopus ID)
Note

QC 20170816

Available from: 2017-08-13 Created: 2017-08-13 Last updated: 2017-11-10Bibliographically approved
Halldin Stenlid, J. & Brinck, T. (2017). Extending the σ-Hole Concept to Metals: An Electrostatic Interpretation of the Nanostructural Effects in Gold and Platinum Catalysis. Journal of the American Chemical Society
Open this publication in new window or tab >>Extending the σ-Hole Concept to Metals: An Electrostatic Interpretation of the Nanostructural Effects in Gold and Platinum Catalysis
2017 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126Article in journal (Refereed) Published
Abstract [en]

Crystalline surfaces of gold are chemically inert, whereas nanoparticles of gold are excellent catalysts for many reactions. The catalytic properties of nanostructured gold have been connected to increased binding affinities of reactant molecules to low-coordinated Au atoms. Here we show that the high reactivity at these sites is a consequence of the formation of σ-holes, i.e. maxima in the surface electrostatic potential (Vs,max) due to the overlap of mainly the valence s-orbitals when forming the bonding σ-orbitals. The σ-holes are binding sites for Lewis bases, and binding energies correlate with magnitudes of the Vs,max. For symmetrical Au clusters, of varying size, the most positive Vs,max are found at corners, edges, and surfaces (facets) and decreasing in that order. This is in agreement with the experimentally and theoretically observed dependence of catalytic activity on local structure. The density of σ-holes can explain the increasing catalytic activity with decreasing particle size also for other transition metal catalysts, such as platinum.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2017
National Category
Physical Chemistry Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-211788 (URN)10.1021/jacs.7b05987 (DOI)000408074800019 ()2-s2.0-85026319771 (Scopus ID)
Note

QC 20170816

Available from: 2017-08-13 Created: 2017-08-13 Last updated: 2017-09-26Bibliographically approved
Stenlid, J. H., Johansson, A. J. & Brinck, T. (2017). Local Lewis Acidity of (TiO2)(n) (n=7-10) Nanoparticles Characterized by DFT-Based Descriptors: Tools for Catalyst Design. The Journal of Physical Chemistry C, 121(49), 27483-27492
Open this publication in new window or tab >>Local Lewis Acidity of (TiO2)(n) (n=7-10) Nanoparticles Characterized by DFT-Based Descriptors: Tools for Catalyst Design
2017 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 49, p. 27483-27492Article in journal (Refereed) Published
Abstract [en]

Transition metal oxide nanoparticles are common materials in a multitude of applications including heterogeneous catalysis, solar energy harvesting, and energy storage. Understanding the particles' interplay with their surroundings is key to their efficient usage and design. Herein two DFT-based descriptors are used to study local reactivity on (TiO2)(n) (n = 7-10) nanoparticles. The local electron attraction energy [E(r)] and the electrostatic potential [V(r)], evaluated on isodensity surfaces, are able to identify and rank Lewis acidic sites on the particles with high accuracy when compared to the interaction energies of the Lewis bases H2O, H2S, NH3, and CO. These interactions are characterized as mainly electrostatically controlled. Given the local character, low computational cost, and excellent performance of the E-s(r) and V-s(r) descriptors, they are anticipated to find widespread use in nanoparticle research and development.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2017
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-220830 (URN)10.1021/acs.jpcc.7b09311 (DOI)000418393900027 ()2-s2.0-85038397134 (Scopus ID)
Note

QC 20180111

Available from: 2018-01-11 Created: 2018-01-11 Last updated: 2018-03-12Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0003-2673-075X

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