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Halldin Stenlid, JoakimORCID iD iconorcid.org/0000-0003-3832-2331
Publications (10 of 15) Show all publications
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
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
Koefoed, L., Vase, K. H., Halldin Stenlid, J., Brinck, T., Yoshimura, Y., Lund, H., . . . Daasbjerg, K. (2017). On the Kinetic and Thermodynamic Properties of Aryl Radicals Using Electrochemical and Theoretical Approaches. CHEMELECTROCHEM, 4(12), 3212-3221
Open this publication in new window or tab >>On the Kinetic and Thermodynamic Properties of Aryl Radicals Using Electrochemical and Theoretical Approaches
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2017 (English)In: CHEMELECTROCHEM, ISSN 2196-0216, Vol. 4, no 12, p. 3212-3221Article in journal (Refereed) Published
Abstract [en]

In this work, sampled-current voltammetry performed on a series of aryldiazonium, diaryliodonium, and triarylsulfonium salts allows the determination of the reduction potential of aryl radicals in acetonitrile. Specifically, this is accomplished by measuring the number of electrons consumed in the reduction process as a function of the applied potential. For the phenyl, 4-bromophenyl, and 4-nitrophenyl radicals, the reduction potential is found to be -0.91 +/- 0.06, -0.90 +/- 0.10, and -0.98 +/- 0.06 V vs. SCE, respectively. Furthermore, from measurements on an extended series of substituted compounds, it is concluded that the substituent effect on the reduction potential is small, which can be explained by the sigma nature of the aryl radical as evidenced from theoretical calculations. At the same time this yields a mean value for the reduction potential of the aryl radical of -0.87 V +/- 0.03 V vs. SCE. Determination of the intrinsic barrier and the standard potential from the data obtained are more uncertain since it is unknown to which extent the competing reference reaction, the electrochemical grafting reaction, is affected by the applied potential. From calculations using density functional theory, the intrinsic barrier for the reduction of the phenyl radical is determined to be 0.32 eV.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2017
Keywords
aryldiazonium salts, density functional calculations, phenyl radicals, reduction potential, sampled-current voltammetry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-221876 (URN)10.1002/celc.201700772 (DOI)000419269000025 ()2-s2.0-85032256466 (Scopus ID)
Note

QC 20180130

Available from: 2018-01-30 Created: 2018-01-30 Last updated: 2018-01-30Bibliographically approved
Halldin Stenlid, J., Johansson, A. J., Kloo, L. & Brinck, T. (2016). Aqueous Solvation and Surface Oxidation of the Cu7 Nanoparticle: Insights from Theoretical Modeling. The Journal of Physical Chemistry C, 120(3), 1977-1988
Open this publication in new window or tab >>Aqueous Solvation and Surface Oxidation of the Cu7 Nanoparticle: Insights from Theoretical Modeling
2016 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 3, p. 1977-1988Article in journal (Refereed) Published
Abstract [en]

The current understanding on: the behavior of nano particles in solution is limited. We have studied tho effects of the aqueous environment on the anoxic oxidation of a Cu-7 riannpartide using a range of different computational solvation models. On the basis of a series of hydroxylated Cu-7(H2O)(y)(OH)x structures, the performance of standard continuum models have been compared to discrete models including up to, and beyond, the second solvation layer. Both full quantum chemical 4 (DFT: PBEO-D3) and QM/MM (PBEO/EPP1) computations were employed in the analysis. The Cu-7 structures were solvated in water nanodroplets and studied by molecular dynamics simulations. On the basis of the simulations, we were able to identify new modes of H2O interactions with the Cu(7)particle, modes that were previously considered unbeneficial. All solvation models favor the "Same equilibrium oxidation state corresponding to a Cu(I)OH surface species. However, for quantitative energy comparison of similar- systems, our results suggest the use of a combined water cinst07cniftinuum model including at least a first explicit solvation shell for energetic comparisons. Nevertheless, the second solvatiOn:thell is -important for identifying representative inner solvation shell structures.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-182781 (URN)10.1021/acs.jpcc.5b11361 (DOI)000369116100069 ()2-s2.0-84956690572 (Scopus ID)
Note

QC 20160223

Available from: 2016-02-23 Created: 2016-02-23 Last updated: 2017-11-30Bibliographically approved
Brinck, T., Carlqvist, P. & Halldin Stenlid, J. (2016). Local Electron Attachment Energy and Its Use for Predicting Nucleophilic Reactions and Halogen Bonding. JOURNAL OF PHYSICAL CHEMISTRY A, 120(50), 10023-10032
Open this publication in new window or tab >>Local Electron Attachment Energy and Its Use for Predicting Nucleophilic Reactions and Halogen Bonding
2016 (English)In: JOURNAL OF PHYSICAL CHEMISTRY A, ISSN 1089-5639, Vol. 120, no 50, p. 10023-10032Article in journal (Refereed) Published
Abstract [en]

A new local property, the local electron attachment energy [E(r)], is introduced and is demonstrated to, be a useful guide to predict intermolecular interactions and chemical reactivity. The E(r) is analogous to the average local ionization energy but indicates susceptibility toward interactions with nucleophiles rather than electrophiles. The functional form E(r) is motivated based on Janak's theorem and the piecewise linear energy dependence of electron addition to atomic and molecular systems. Within the generalized Kohn-Sham method (GKS-DFT), only the virtual orbitals with negative eigenvalues contribute to E(r). In the, present study, E(r) has been computed from orbitals obtained from GKS-DFT computations with a hybrid exchange correlation functional. It is shown that E(r) computed on a molecular isodengty surface, E-S(r), reflects the regioselectivity and relative reactivity for nucleophilic aromatic substitution, nucleophilic addition to activated double bonds, and formation of halogen bonds. Good to excellent correlations between experimental or theoretical measures of interaction strengths and minima in E-S(r) (E-S,E-min) are demonstrated.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-200209 (URN)10.1021/acs.jpca.6b10142 (DOI)000390735700014 ()
Funder
Swedish Research Council
Note

QC 20170202

Available from: 2017-02-02 Created: 2017-01-23 Last updated: 2017-08-28Bibliographically approved
Soldemo, M., Halldin Stenlid, J., Besharat, Z., Ghadami Yazdi, M., Önsten, A., Leygraf, C., . . . Weissenrieder, J. (2016). The Surface Structure of Cu2O(100). The Journal of Physical Chemistry C, 120(8), 4373-4381
Open this publication in new window or tab >>The Surface Structure of Cu2O(100)
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2016 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 8, p. 4373-4381Article in journal (Refereed) Published
Abstract [en]

Despite the industrial importance of copper oxides, the nature of the (100) surface of Cu2O has remained poorly understood. The surface has previously been subject to several theoretical and experimental studies, but has until now not been investigated by atomically resolved microscopy or high-resolution photoelectron spectroscopy. Here we determine the atomic structure and electronic properties of Cu2O(100) by a combination of multiple experimental techniques and simulations within the framework of density functional theory (DFT). Low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM) characterized the three ordered surface structures found. From DFT calculations, the structures are found to be energetically ordered as (3,0;1,1), c(2 x 2), and (1 x 1) under ultrahigh vacuum conditions. Increased oxygen pressures induce the formation of an oxygen terminated (1 x 1) surface structure. The most common termination of Cu2O(100) has previously been described by a (3 root 2 x root 2)R45 degrees unit cell exhibiting a LEED pattern with several missing spots. Through atomically resolved STM, we show that this structure instead is described by the matrix (3,0;1,1). Both simulated STM images and calculated photoemission core level shifts compare favorably with the experimental results.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-184532 (URN)10.1021/acs.jpcc.5b11350 (DOI)000371562000024 ()2-s2.0-84960171601 (Scopus ID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

QC 20160406

Available from: 2016-04-06 Created: 2016-04-01 Last updated: 2017-11-30Bibliographically approved
Halldin Stenlid, J., Johansson, A. J. & Brinck, T. (2014). Searching for the thermodynamic limit - a DFT study of the step-wise water oxidation of the bipyramidal Cu-7 cluster. Physical Chemistry, Chemical Physics - PCCP, 16(6), 2452-2464
Open this publication in new window or tab >>Searching for the thermodynamic limit - a DFT study of the step-wise water oxidation of the bipyramidal Cu-7 cluster
2014 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 16, no 6, p. 2452-2464Article in journal (Refereed) Published
Abstract [en]

Oxidative degradation of copper in aqueous environments is a major concern in areas such as catalysis, electronics and construction engineering. A particular challenge is to systematically investigate the details of this process for non-ideal copper surfaces and particles under the conditions found in most real applications. To this end, we have used hybrid density functional theory to study the oxidation of a Cu-7 cluster in water solution. Especially, the role of a large water coverage is explored. This has resulted in the conclusion that, under atmospheric H-2 pressures, the thermodynamically most favored state of degradation is achieved upon the generation of four H-2 molecules (i.e. Cu-7 + 8H(2)O -> Cu-7(OH)(8) + 4H(2)) in both condensed and gas phases. This state corresponds to an average oxidation state below Cu(I). The calculations suggest that the oxidation reaction is slow at ambient temperatures with the water dissociation as the rate-limiting step. Our findings are expected to have implication for, among other areas, the copper catalyzed water-gas shift reaction, and for the general understanding of copper corrosion in aqueous environments.

Keywords
Gas Shift Reaction, Small Copper Clusters, Continuum Dielectric Theory, Solvation Free-Energies, Near-Ambient Conditions, Ab-Initio, Dissociative Adsorption, Structure Sensitivity, Hyperfine-Structure, Fundamental-Aspects
National Category
Physical Sciences Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-141318 (URN)10.1039/c3cp53865f (DOI)000329926700032 ()2-s2.0-84892606991 (Scopus ID)
Note

QC 20140214

Available from: 2014-02-14 Created: 2014-02-13 Last updated: 2017-12-06Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0003-3832-2331

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