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  • 1.
    Ayub, Rabia
    et al.
    Uppsala University, Sweden.
    El Bakouri, O.
    Smith, J. R.
    Jorner, K.
    Ottosson, H.
    Triplet State Baird Aromaticity in Macrocycles: Scope, Limitations, and Complications2021Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 125, nr 2, s. 570-584Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The aromaticity of cyclic 4nπ-electron molecules in their first ππ∗ triplet state (T1), labeled Baird aromaticity, has gained growing attention in the past decade. Here we explore computationally the limitations of T1 state Baird aromaticity in macrocyclic compounds, [n]CM's, which are cyclic oligomers of four different monocycles (M = p-phenylene (PP), 2,5-linked furan (FU), 1,4-linked cyclohexa-1,3-diene (CHD), and 1,4-linked cyclopentadiene (CPD)). We strive for conclusions that are general for various DFT functionals, although for macrocycles with up to 20 π-electrons in their main conjugation paths we find that for their T1 states single-point energies at both canonical UCCSD(T) and approximative DLPNO-UCCSD(T) levels are lowest when based on UB3LYP over UM06-2X and UCAM-B3LYP geometries. This finding is in contrast to what has earlier been observed for the electronic ground state of expanded porphyrins. Yet, irrespective of functional, macrocycles with 2,5-linked furans ([n]CFU's) retain Baird aromaticity until larger n than those composed of the other three monocycles. Also, when based on geometric, electronic and energetic aspects of aromaticity, a 3[n]CFU with a specific n is more strongly Baird-aromatic than the analogous 3[n]CPP while the magnetic indices tell the opposite. To construct large T1 state Baird-aromatic [n]CM's, the design should be such that the T1 state Baird aromaticity of the macrocyclic perimeter dominates over a situation with local closed-shell Hückel aromaticity of one or a few monocycles and semilocalized triplet diradical character. Monomers with lower Hückel aromaticity in S0 than benzene (e.g., furan) that do not impose steric congestion are preferred. Structural confinement imposed by, e.g., methylene bridges is also an approach to larger Baird-aromatic macrocycles. Finally, by using the Zilberg-Haas description of T1 state aromaticity, we reveal the analogy to the Hückel aromaticity of the corresponding closed-shell dications yet observe stronger Hückel aromaticity in the macrocyclic dications than Baird aromaticity in the T1 states of the neutral macrocycles. © 2021 The Authors.

  • 2.
    Bergenståhl, B
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Stenius, P
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Phase equilibria of dioleoulphosphatidylcholine with formamide methylformamide and dimethylformamide1987Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 91, s. 5944-5948Artikel i tidskrift (Refereegranskat)
  • 3. Chachaty, C
    et al.
    Warr, GG
    Jansson, M
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Li, P
    Influence of the polar head size on the dynamics of micellized surfactants1991Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 95, s. 3830-3836Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The dynamics of micellized quaternary ammonium surfactants has been investigated by means of the frequency dependence of the 13C longitudinal relaxation rates. Trimethyl-, triethyl-, and tributyldodecylammonium bromides were used to systematically vary the bulk of the polar head and examine its influence on the internal and overall motions of the surfactants. The relaxation data were analyzed by means of the two-step model and of a rotational jump model relevant to the trans-gauche isomerizations about the bonds. In the case of the trimethyldodecyl--ammonium bromide an excellent agreement is obtained by the two-step model as the vicinity of the nitrogen is well above the values expected for methylene groups. The jump model shows that this behavior results from a slowing of the internal motions beyond the domain of validity of the two-step model.

  • 4. Christenson, HK
    et al.
    Claesson, PM
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Berg, J
    Herder, PC
    Forces between fluorocarbon surfactant monolayers: salt effects on the hydrophobic interaction1989Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 93, s. 1472-1478Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    Further studies of the hydrophobic attraction between fluorocarbon surfaces in water have been carried out, including (i) a comparison between surfaces prepared by Langmuir-Blodgett deposition and by adsorption from solution using the same surfactant and (ii) the effect of added electrolyte. In general, the surfaces prepared by deposition show the longest range of the attraction - measurable at 80-90 nm with an exponential decay length of about 15 nm at separations above 5 nm. In the case of adsorbed monolayers incomplete adsorption or additional adsorption to the hydrophobic monolayer surfaces often leads to an effective attraction that is of considerably shorter range. Under optimal conditions, however, adsorbed monolayers give an attraction of a similar range. In both cases the interaction becomes more attractive at small separations and appears to decay exponentially with a decay length of 2-3 nm below about 15 nm. The deposited fluorocarbon monolayers are unstable in sodium or potassium salt solution but remain intact in terapentylammonium bromide. With increasing concentration of this salt the range of the hydrophobic interaction decreases as more and more ions adsorb to the surfaces. The short-range interaction seems to be less sensitive to the presence of electrolyte - the adhesion at contact shows a much less dramatic decrease with increasing electrolyte concentration. Nevertheless, the measured electrolyte dependence of the hydrphobic interaction is at least partly due to the surfaces becoming less hydrophobic themselves, as reflected by their caviation bahaviour.

  • 5.
    Claesson, P
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Carmona-Ribeiro, AM
    Kurihara, K
    Dihexadecyl phosphate monolayers: Intralayer and Interlayer Interactions1989Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 93, s. 917-922Artikel i tidskrift (Refereegranskat)
  • 6.
    Claesson, P
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Christenson, H
    Very long range attractive forces between uncharged hydrocarbon and fluorocarbon surfaces in water1988Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 92, s. 1650-1655Artikel i tidskrift (Refereegranskat)
  • 7.
    Dahlgren, MAG
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Waltermo, Å
    Blomberg, E
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Claesson, PM
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Sjöström, L
    Åkesson, T
    Salt effects on the interaction between adsorbed cationic polyelectrolyte layers - Theory and experiment1993Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 97, s. 11769-11775Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The effect of inert salt concentration on polyelectrolyte adsorption from aqueous solutions onto oppositely charged surfaces, and the interactions between such surfaces were studied experimentally using a surface force technique and compared to theoretical predictions from Monte Carlo simulations. At a polyelectrolyte concentration of 10 ppm and a low inert salt concentration (10-4 M) the polyelectrolytes adsorb in a flat conformation and the force acting between the surfaces is close to zero down to a separation of 10-15 nm, where the surfaces jump inwards. The attractive force observed at separations below 10 nm is stronger than the expected van der Waals force. The magnitude and range of the attraction agrees with forces obtained from Monte Carlo simulation and we interpret the attraction as being due to bridging polyelectrolytes. When the salt concentration is increased, additional polyelectrolyte adsorption takes place. This gives again rise to a repulsive force, which is significantly larger than what is observed between bare surfaces. The extra repulsion is due to adsorbed polyelectrolytes stretching out from the surfaces and is also predicted from simulations.

  • 8.
    Friberg, S
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Ahmad, SI
    Kinetics of the catalysis by reversed micelles of cetyltrimethylammonium bromide in hexanol1971Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 75, s. 2001-2004Artikel i tidskrift (Refereegranskat)
  • 9.
    Friberg, S
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Rydhag, L
    Lindblom, G
    Catalysis of p-nitrophenol laurate hydrolysis in solution showing transition from reversed to normal micelles1973Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 77, s. 1280-1283Artikel i tidskrift (Refereegranskat)
  • 10. Gestblom, B
    et al.
    Noreland, E
    Sjöblom, J
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    A precision dielectric time domain spectroscopy method in the gigahertz range1987Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 91, s. 6329-6331Artikel i tidskrift (Refereegranskat)
  • 11. Gestblom, B
    et al.
    Sjöblom, J
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Dielectric properties of 1,2-diol solutions with water or electrolytes1986Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 90, s. 4175-4178Artikel i tidskrift (Refereegranskat)
  • 12. Jonströmer, M
    et al.
    Sjöberg, M
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Wärnheim, T
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Aggregation and solvent interaction in nonionic surfactant systems with formamide1990Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 94, s. 7549-7555Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The self-association and solvent interaction of some polyethylene glycol alkyl ether surfactants (CxEy) in fornamide have been studied via determinations of phase diagrams and NMR self-diffusion measurements. For C12E3 and C12 E4, small micelles but no liquid chrystalline phases form. Increasing the alkyl chain length to hexadecyl (C16E4, C16E6, and C16E8), mesophase formation occurs analogously to the corresponding aqueous system. No aggregate growth occurs in the micellar phase, neither at high temperatures and high surfactant concentrations nor when approaching the lower consolute temperature. The solvent diffusion was analyzed within the cell diffusion model, and a concentration-independent amount of 1-5 and probably not more than 3 formamide molecules was found to interact with each ethylene oxide group. Furthermore, the calculations indicated a ploymer-like state of the micellar headgroup shell, with a slight decrease of the formamide content therein at a raised temperature. In conclusion, the behaviour of CxEy/formamide systems is qualitatively similar to that of the corresponding aqueous sytem.

  • 13.
    Langer, Sarka
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, SP – Sveriges Tekniska Forskningsinstitut / Organisk kemi (Kmo).
    Characterization of HOCI Using Atmospheric Pressure Ionization Mass Spectrometry1999Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 103, nr 41, s. 8231-8238Artikel i tidskrift (Övrigt vetenskapligt)
  • 14.
    Langer, Sarka
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, SP – Sveriges Tekniska Forskningsinstitut / Organisk kemi (Kmo).
    Kinetics of the gas-phase reaction of some unsaturated alcohols with the nitrate radical2002Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 106, s. 945-951Artikel i tidskrift (Övrigt vetenskapligt)
  • 15. Parker, JL
    et al.
    Cho, DL
    Claesson, PM
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Plasma modification of mica; forces between fluorocarbon surfaces in water and a nonpolar liquid1989Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 93, s. 6121-6125Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    Mica has been exposed to low-temperature water vapor plasma. A combination of reaction and sputtering in the plasma environment alters the surface properties of mica and activates the surface toward with chlorosilanes. The plasma treatment technique causes minimal alteration to the surface smoothness and oscillatory solvation forces were measured in octamethylcyclotetrasiloxane (OMCTS). Reaction of the plasma-treated mica with (tridecaflouro-1,1,2,2-tetrahydrooctyl)-1-dimethylchlorosilane renders the surface hydrophobic. The oscillatory solvation force is removed by surface roughness, due to a low surface density of reacted silane ( one molecule per 5 nm2 as estimated by ESCA) and the forces between thesesurfaces in OMCTS were attractive and in agreement with the force expected from van der Waals theory. The force between two silanated surfaces in water is in good agreement with the force calculated from DLVO theory at separations greater than 50 nm but an additional exponential attraction is observed at smaller separations. The magnitude and decay length of this attraction are in close agreement with those found previously between mica surfaces hydrophobed by Langmuir-Blodgett deposition of surfactant monolayers. Consequently, the hydrophobic interaction observed between surfactant-coated surfaces does not result from instabilities in the surfactant layer.

  • 16. Parker, JL
    et al.
    Claesson, PM
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Attard, P
    Bubbles, cavities, and the long-ranged attraction between hydrophobic surfaces1994Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 98, s. 8468-8480Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    Measurements of the forces in water between neutral hydrophobic surfaces prepared by covalent modification of glass are presented. The surfaces are stable under a variety of conditions including high temperature, high salt concentrations and with added ethanol. The forces between these surfaces have been studied under all of these different conditions. In water the force is attractive at very large surface separations, and discontinuities or steps are present in the force curves. It is suggested that the steps at the onset of the force are due to the bridging of submicroscopic bubbles or cavities between the surfaces and that it is their consequent growth with decreasing separation that causes the long-range attraction between hydrophobic surfaces. Electrolyte has a negligible effect on the range and strength of the measured forces, except at very high salt concentrations where the strength of the attractive forces and the adhesion between the surfaces increases slightly. The addition of ethanol reduces both the strength of the long range forces and the adhesion between the surfaces. On the basis of the comparison between these results and earlier measurements, it appears that the attraction does not obey the Derjaguin approximation. Forces were also measured in the presence of a microscopic vapor cavity created by first bringing the surfaces into contact.

  • 17. Parker, JL
    et al.
    Yaminsky, VV
    Claesson, PM
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Surface forces between glass surfaces in cetyltrimethylammonium bromide solutions1993Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 97, s. 7706-7710Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    A new surface apparatus has been used to study the interactions between glass surfaces immersed in CTAB (cetyltrimethylammonium bromide) solutions. At low surfactant concentrations CTAB adsorbs to form a monolayer, and the surfaces become adhesive in contact. At a concentration of 5 x 10-5 M the charge on glass is neutralized, and the surfaces experience an attractive force in excess of that expected from van der Waals interactions. At concentrations just below the critical micelle concentration, CTAB adsorbs to the hydrophobic interface to form loosely packed bilayers, but the surfaces always come to an adhesive minimum. These observations are quite different from those made when mica is used as the substrate. A comparison between the results obtained for the two substrates is made, and the reasons for the differences are discussed. Glass has a lower area per charge compared with mica, and this results in less tightly packed monolayers and in turn bilayers on glass when compared with mica.

  • 18. Persson, M
    et al.
    Stenius, P
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Ström, G
    Ödberg, L
    Solubilization, micellization and phase equilibria of polyoxyethylene derivatives of dehydroabietic acid1980Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 84, s. 1557-1560Artikel i tidskrift (Refereegranskat)
  • 19. Pezron, I
    et al.
    Pezron, E
    Bergenståhl, B
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Claesson, P
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Repulsive pressure between monoglyceride bilayers in the lamellar and gel states1990Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 94, s. 8255-8261Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The swelling pressure of two different monoglycerides, monoolein and monopalmetin, has been investigated at different temperatures through the analysis of water vapour pressure data obtained by head-space gas chromatography. The structural characteristics of the lamellar and gel phases of monoglyceride-water mixtures were determined by low-angle X-ray diffraction. In the lamellar phase, a strong repulsive force is observed., which is not very dependent on the type of monoglyceride or on the temperature. In the gel phase, the repulsive pressure is significantly lower. The range of the swelling pressure is less than for phospholipids (about 10 Å for monoglyceridews and 20-30 Å for phospholipids), demonstrating the decisive rule of the polar head-group. A comparison with the forces acting between monoglyceride layers deposited on solid surfaces, measured by a surface force apparatus, reveals a qualitative agreement bvetween the two techniques. The most significant difference is that the repulsive force at short separations (<5 Å) is lower between deposited layers than between free bilayers.

  • 20. Saris, P
    et al.
    Rosenholm, JB
    Sjöblom, E
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Henriksson, U
    A thermometric investigation of the association equilibria of alcohols in hydrocarbons1986Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 90, s. 660-665Artikel i tidskrift (Refereegranskat)
  • 21. Silveston, R
    et al.
    Kronberg, B
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Water structuring around nonpolar molecules as determined by HPLC1989Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 93, s. 6241-6246Artikel i tidskrift (Refereegranskat)
  • 22.
    Sjöblom, E
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Henriksson, U
    Sodium-23 and hydrogen-2 nuclear magnetic resonance study of microemulsionscontaining sodium oleate1982Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 86, s. 4451-4456Artikel i tidskrift (Refereegranskat)
  • 23. Sjöblom, E
    et al.
    Jönsson, B
    Jönsson, A
    Stenius, P
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Saris, P
    Ödberg, L
    Microemulsions in the system sodium p-octylbenzenesulfonate/butanol/water/hydrocarbons : phase diagrams and vapor pressures1986Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 90, s. 119-124Artikel i tidskrift (Refereegranskat)
  • 24.
    Wärnheim, T
    et al.
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Sjöblom, E
    RISE., SP – Sveriges Tekniska Forskningsinstitut, SP Sveriges tekniska forskningsinstitut, YKI – Ytkemiska institutet.
    Henriksson, U
    Stilbs, P
    Phase diagrams and self-diffusion behaviour in ionic microemulsion systems containing different cosurfactants1984Ingår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 88, s. 5420-5425Artikel i tidskrift (Refereegranskat)
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