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Publications (10 of 118) Show all publications
Izquierdo, J., Demurget, N., Landa, A., Brinck, T., Mercero, J. M., Dinér, P., . . . Palomo, C. (2019). Asymmetric Synthesis of Adjacent Tri- and Tetrasubstituted Carbon Stereocenters: Organocatalytic Aldol Reaction of an Hydantoin Surrogate with Azaarene 2-Carbaldehydes. Chemistry - A European Journal
Open this publication in new window or tab >>Asymmetric Synthesis of Adjacent Tri- and Tetrasubstituted Carbon Stereocenters: Organocatalytic Aldol Reaction of an Hydantoin Surrogate with Azaarene 2-Carbaldehydes
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2019 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765Article in journal (Refereed) Published
Abstract [en]

A bifunctional amine/squaramide catalyst promoted direct aldol addition of an hydantoin surrogate to pyridine 2-carbaldehyde N-oxides to afford adducts bearing two vicinal tertiary/quaternary carbons in high diastereo- and enantioselectivity (d.r. up to >20:1; ee up to 98 %) is reported. Acid hydrolysis of adducts followed by reduction of the N-oxide group yields enantiopure carbinol-tethered quaternary hydantoin-azaarene conjugates with densely functionalized skeletons. DFT studies of the potential energy surface (B3LYP/6-31+G(d)+CPCM (dichloromethane)) of the reaction correlate the activity of different catalysts and support an intramolecular hydrogen-bond-assisted activation of the squaramide moiety in the transition state of the catalytic reaction.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2019
Keywords
asymmetric catalysis, azaarenes, Bronsted bases, hydantoins, quaternary stereocenters
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-261019 (URN)10.1002/chem.201902817 (DOI)000484834700001 ()31318987 (PubMedID)2-s2.0-85072225163 (Scopus ID)
Note

QC 20191010

Available from: 2019-10-10 Created: 2019-10-10 Last updated: 2019-10-10Bibliographically approved
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
Tissot, H., Wang, C., Stenlid, J. H., Panahi, M., Kaya, S., Soldemo, M., . . . Weissenrieder, J. (2019). Interaction of Atomic Hydrogen with the Cu2O(100) and (111) Surfaces. The Journal of Physical Chemistry C, 123(36), 22172-22180
Open this publication in new window or tab >>Interaction of Atomic Hydrogen with the Cu2O(100) and (111) Surfaces
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2019 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 123, no 36, p. 22172-22180Article in journal (Refereed) Published
Abstract [en]

Reduction of Cu2O by hydrogen is a common preparation step for heterogeneous catalysts; however, a detailed understanding of the atomic reaction pathways is still lacking. Here, we investigate the interaction of atomic hydrogen with the Cu2O(100):(3,0;1,1) and Cu2O(111):(root 3 x root 3)R30 degrees surfaces using scanning tunneling microscopy (STM), low-energy electron diffraction, temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). The experimental results are compared to density functional theory simulations. At 300 K, we identify the most favorable adsorption site on the Cu2O(100) surface: hydrogen atoms bind to an oxygen site located at the base of the atomic rows intrinsic to the (3,0;1,1) surface. The resulting hydroxyl group subsequently migrates to a nearby Cu trimer site. TPD analysis identifies H-2 as the principal desorption product. These observations imply that H-2 is formed through a disproportionation reaction of surface hydroxyl groups. The interaction of H with the (111) surface is more complex, including coordination to both Cu+ and O-CUS sites. STM and XPS analyses reveal the formation of metallic copper clusters on the Cu2O surfaces after cycles of hydrogen exposure and annealing. The interaction of the Cu clusters with the substrate is notably different for the two surface terminations studied: after annealing, the Cu clusters coalesce on the (100) termination, and the (3,0;1,1) reconstruction is partially recovered. Clusters formed on the (111) surface are less prone to coalescence, and the (root 3 x root 3)R30 degrees reconstruction was not recovered by heat treatment, indicating a weaker Cu cluster to support interaction on the (100) surface.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-261961 (URN)10.1021/acs.jpcc.9b03888 (DOI)000486360900036 ()2-s2.0-85072714617 (Scopus ID)
Note

QC 20191015

Available from: 2019-10-15 Created: 2019-10-15 Last updated: 2019-10-15Bibliographically approved
Halldin Stenlid, J., Johansson, A. J. & Brinck, T. (2019). The local electron attachment energy and the electrostatic potential as descriptors of surface-adsorbate interactions. Physical Chemistry, Chemical Physics - PCCP, 21(31), 17001-17009
Open this publication in new window or tab >>The local electron attachment energy and the electrostatic potential as descriptors of surface-adsorbate interactions
2019 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 21, no 31, p. 17001-17009Article in journal (Refereed) Published
Abstract [en]

Two local reactivity descriptors computed by Kohn-Sham density functional theory (DFT) are used to predict and rationalize interactions of nucleophilic molecules (exemplified by CO and H2O) with transition metal (TM) and oxide surfaces. The descriptors are the electrostatic potential, V-S(r), and the local electron attachment energy, E-S(r), evaluated on surfaces defined by the 0.001 e Bohr(-3) isodensity contour. These descriptors have previously shown excellent abilities to predict regioselectivity and rank molecular as well as nanoparticle reactivities and interaction affinities. In this study, we generalize the descriptors to fit into the framework of periodic DFT computations. We also demonstrate their capabilities to predict local surface propensity for interaction with Lewis bases. It is shown that E-S(r) and V-S(r) can rationalize the interaction behavior of TM oxides and of fcc TM surfaces, including low-index, stepped and kinked surfaces spanning a wide range of interaction sites with varied coordination environments. Broad future applicability in surface science is envisaged for the descriptors, including heterogeneous catalysis and electrochemistry.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-257432 (URN)10.1039/c9cp03099a (DOI)000479245800008 ()31346592 (PubMedID)2-s2.0-85070695947 (Scopus ID)
Note

QC 20190902

Available from: 2019-09-02 Created: 2019-09-02 Last updated: 2019-09-02Bibliographically 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
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ORCID iD: ORCID iD iconorcid.org/0000-0003-2673-075X

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