| 51. |
- Baryshnikova, A. T., et al.
(författare)
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Computational study of the structure and magnetic properties of the weakly-coupled tetranuclear square-planar complex of Cu(II) with a tetraporphyrin sheet
- 2019
-
Ingår i: Inorganica Chimica Acta. - : Elsevier S.A.. - 0020-1693 .- 1873-3255. ; 485, s. 73-79
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Tidskriftsartikel (refereegranskat)abstract
- Owing to the fact that weakly-coupled Cu(II) complexes are potentially applicable in the fields of spintronics and single-molecule magnets we have studied one particularly conspicuous case – a tetranuclear square-planar complex of Cu(II) ions with a π-extended tetraporphyrin ligand (Tetrahedron, 2008, 64, 11433), the structural criteria of which, with very long distances between the paramagnetic centers, can sensibly define the exchange coupling constants and magnetic behaviour. We use the “broken symmetry” density functional theory formalism for various spin states (open-shell singlet, triplet and quintet states). The calculated value of the magnetic exchange integral corresponds to a very weak antiferromagnetic coupling between the neighboring Cu(II) ions (Jcalc = –1.48 cm−1(calculated) Jexp = −1.16 cm−1 (experiment)). The opposite Cu(II) ions are coupled ferromagnetically with an extremely small exchange constant (jcalc = 0.09 cm−1 (calculated) that corresponds to the open-shell singlet ground state of the following spin configuration↑↓↑↓. The exchange mechanism between the [Cu(n) + 4N] localized singly-occupied “magnetic” orbitals of the dxy(Cu) + 4sp2(N) nature indicates a diffuse non-zero overlap between them on the Carbon atoms of the organic ligand. The numerical analysis of atomic spin densities and corresponding decomposition coefficients for the singly-occupied “magnetic” orbitals confirm the proposed exchange mechanism. This superexchange pathway is mediated by the in-plane sp2-hybrid orbitals of the Carbon atoms that couple four [Cu + 4N] fragments by the σ-bond system. For more detailed characterization of the target system a topological analysis of electron density distributions in the high-spin quintet states has been carried out using the Bader's method “quantum theory of atoms in molecules”.
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| 52. |
- Bednarska, Joanna, et al.
(författare)
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Elucidating the Mechanism of Zn2+ Sensing by a Bipyridine Probe Based on Two-Photon Absorption
- 2016
-
Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 120:34, s. 9067-9075
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Tidskriftsartikel (refereegranskat)abstract
- In this work, we examine, by means of computational methods, the mechanism of Zn2+ sensing by a bipyridine-centered, D-pi-A-pi-D-type-ratiometric molecular probe. According to recently published experimental data [Divya, K. P.; Sreejith, S.; Ashokkumar, P.; Yuzhan, K.; Peng, Q; Maji, S. K.; Tong, Y.; Yu, H.; Zhao, Y.; Ramamurthy, P.; Ajayaghosh, A. A ratiometric fluorescent molecular -probe with enhanced two-photon response upon Zn2+ binding for in vitro and in vivo: bioimaging.= Chem. Sci. 2014, S, 3469-3474], after coordination to zinc ions the -probe exhibits a large enhancement of the two -photon absorption cross section. The goal of our investigation was to elucidate the mechanism behind this phenomenon. For this purpose, linear and nonlinear optical properties of -the unbound (cation-free) and bound probe were calculated, including the influence of solute Solvent interactions, implicitly using a polarizable continuum model and exp-licitely employing the QM/MM approach. Because the results of the calculations indicate that many conformers of the probe are energetically accessible at room temperature in solution and hence contribute to the Signal, structurepteperty relationships were also taken into account. Results of our simulations-demonstrate that the one-photon absorption bands for both the unbound -and bound forms correspond to the bright pi -> pi* transition to the first excited state; which, on the other hand,. exhibits negligible two-photon activity. On the basis of the results of the quadratic respOnse calculations, we put forward-notion that it is the second excited state that gives the strong signal in the experimental nonlinear spectrum. To explain the differenCes in the two-photon absorption activity for the two lowest-lying excited states and nonlinear response enhancement upon binding, we employed the generalized few -state model including the ground, first, and- second excited states. The analysis of the optical channel suggests that the large two-photon response is due to the coordination -induced increase of the, transition- moment from the first to the second excited state.
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| 53. |
- Bednarska, Joanna, et al.
(författare)
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Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution : Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones
- 2017
-
Ingår i: Molecules. - : MDPI AG. - 1431-5157 .- 1420-3049. ; 22:10
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Tidskriftsartikel (refereegranskat)abstract
- We have examined several approaches relying on the Polarizable Embedding (PE) scheme to predict optical band shapes for two chalcone molecules in methanol solution. The PE-TDDFT and PERI-CC2 methods were combined with molecular dynamics simulations, where the solute geometry was kept either as rigid, flexible or partly-flexible (restrained) body. The first approach, termed RBMD-PE-TDDFT, was employed to estimate the inhomogeneous broadening for subsequent convolution with the vibrationally-resolved spectra of the molecule in solution determined quantum-mechanically (QM). As demonstrated, the RBMD-PE-TDDFT/QM-PCM approach delivers accurate band widths, also reproducing their correct asymmetric shapes. Further refinement can be obtained by the estimation of the inhomogeneous broadening using the RBMD-PERI-CC2 method. On the other hand, the remaining two approaches (FBMD-PE-TDDFT and ResBMD-PE-TDDFT), which lack quantum-mechanical treatment of molecular vibrations, lead to underestimated band widths. In this study, we also proposed a simple strategy regarding the rapid selection of the exchange-correlation functional for the simulations of vibrationally-resolved one-and two-photon absorption spectra based on two easy-to-compute metrics.
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| 54. |
- Bednarska, Joanna, et al.
(författare)
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Two-photon absorption of BF2-carrying compounds : insights from theory and experiment
- 2017
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 19:8, s. 5705-5708
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Tidskriftsartikel (refereegranskat)abstract
- This communication presents a structure-property study of a few novel pyridine-based difluoroborate compounds with a N-BF2-O core, which exhibit outstanding fluorescence properties. To exploit their potential for two-photon bioimaging, relationships between the two-photon action cross section and systematic structural modifications have been investigated and unravelled.
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| 55. |
- Begunovich, Lyudmila V., et al.
(författare)
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Single-layer polymeric tetraoxa[8]circulene modified by s-block metals : toward stable spin qubits and novel superconductors
- 2021
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Ingår i: Nanoscale. - : Royal Society of Chemistry. - 2040-3364 .- 2040-3372. ; 13:9, s. 4799-4811
-
Tidskriftsartikel (refereegranskat)abstract
- Tunable electronic properties of low-dimensional materials have been the object of extensive research, as such properties are highly desirable in order to provide flexibility in the design and optimization of functional devices. In this study, we account for the fact that such properties can be tuned by embedding diverse metal atoms and theoretically study a series of new organometallic porous sheets based on two-dimensional tetraoxa[8]circulene (TOC) polymers doped with alkali or alkaline-earth metals. The results reveal that the metal-decorated sheets change their electronic structure from semiconducting to metallic behaviour due to n-doping. Complete active space self-consistent field (CASSCF) calculations reveal a unique open-shell singlet ground state in the TOC-Ca complex, which is formed by two closed-shell species. Moreover, Ca becomes a doublet state, which is promising for magnetic quantum bit applications due to the long spin coherence time. Ca-doped TOC also demonstrates a high density of states in the vicinity of the Fermi level and induced superconductivity. Using the ab initio Eliashberg formalism, we find that the TOC-Ca polymers are phonon-mediated superconductors with a critical temperature T-C = 14.5 K, which is within the range of typical carbon based superconducting materials. Therefore, combining the proved superconductivity and the long spin lifetime in doublet Ca, such materials could be an ideal platform for the realization of quantum bits.
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| 56. |
- Belyanin, Maxim L., et al.
(författare)
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Design, synthesis and evaluation of a new Mn - Contrast agent for MR imaging of myocardium based on the DTPA-phenylpentadecanoic acid complex
- 2016
-
Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 665, s. 111-116
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Tidskriftsartikel (refereegranskat)abstract
- In the present paper we describe the first synthesis and evaluation of a novel Mn (II) complex (DTPA-PPDA Mn (II)) which contains a C-15 fatty acid moiety that has high affinity to the heart muscle. The complexation energy of DTPA-PPDA Mn (II) evaluated by quantum chemistry methodology indicates that it essentially exceeds the corresponding value for the known DTPA Mn (II) complex. Molecular docking revealed that the affinity of the designed complex to the heart-type transport protein H-FABP well exceeds that of lauric acid. Phantom experiments in low-field MRI the designed contrast agent provides MR imaging comparable to gadopentetic acid.
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| 57. |
- Bergersen, Henrik, 1978-
(författare)
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Free Neutral Clusters and Liquids Studied by Electron Spectroscopy and Lineshape Modeling
- 2008
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The electronic and geometrical structure of free neutral clusters and liquids have been studied using synchrotron-radiation based photoelectron and Auger electron spectroscopy in combination with lineshape modeling. A novel experimental setup has been developed for studies of liquids, based on the liquid microjet technique. Theoretical lineshapes have been computed using both classical (molecular dynamics) and quantum mechanical (mainly density functional theory) methods.Clusters are finite ensembles of atoms or molecules, ranging in size from a few to several thousand atoms. Apart from being fundamentally interesting, clusters are also promising as building blocks for nano-technology. In this thesis results are presented for rare-gas and molecular clusters, ranging from weakly van-deer-Waals bonded to hydrogen bonded. It is shown that the combination of core-level photoelectron spectroscopy (XPS) and lineshape modeling can be used to estimate the sizes of clusters. A model for treating the effect of inter-molecular nuclear relaxation upon ionization is proposed. The structure of single-component molecular clusters are investigated by molecular dynamics simulations, validated against XPS data. Finally, the radial structure of a two-component molecular cluster is investigated by XPS.Liquids have been studied for centuries, but still many questions remain regarding the microscopic properties. With the recent development of the liquid microjet technique, new insight into the atomic structure can be obtained. In this thesis we study aqueous solutions using photoelectron and Auger electron spectroscopy (AES). We investigate the structure of surface active molecules by XPS, study the Auger decay after core-level ionization in aqueous potassium chloride (KCl), and follow the changes in molecular structure of glycine as a function of pH.
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| 58. |
- Bergstrand, Jan, et al.
(författare)
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On the decay time of upconversion luminescence
- 2019
-
Ingår i: Nanoscale. - : Royal Society of Chemistry. - 2040-3364 .- 2040-3372. ; 11:11, s. 4959-4969
-
Tidskriftsartikel (refereegranskat)abstract
- In this study, we systematically investigate the decay characteristics of upconversion luminescence (UCL) under anti-Stokes excitation through numerical simulations based on rate-equation models. We find that a UCL decay profile generally involves contributions from the sensitizer's excited-state lifetime, energy transfer and cross-relaxation processes. It should thus be regarded as the overall temporal response of the whole upconversion system to the excitation function rather than the intrinsic lifetime of the luminescence emitting state. Only under certain conditions, such as when the effective lifetime of the sensitizer's excited state is significantly shorter than that of the UCL emitting state and of the absence of cross-relaxation processes involving the emitting energy level, the UCL decay time approaches the intrinsic lifetime of the emitting state. Subsequently, Stokes excitation is generally preferred in order to accurately quantify the intrinsic lifetime of the emitting state. However, possible cross-relaxation between doped ions at high doping levels can complicate the decay characteristics of the luminescence and even make the Stokes-excitation approach fail. A strong cross-relaxation process can also account for the power dependence of the decay characteristics of UCL.
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| 59. |
- Birgerson, J., et al.
(författare)
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A study of the electronic structure of ethylenedioxythiophene in gas phase using NEXAFS and quantum chemical calculations
- 2004
-
Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 392:1-3, s. 100-104
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Tidskriftsartikel (refereegranskat)abstract
- Near-edge X-ray absorption fine structure spectroscopy spectra of ethylenedioxythiophene has been recorded in gas phase at the carbon K-edge, sulphur L-edge and oxygen, K-edge. The experimental data has been interpreted with the help of a modified density functional code deMon. The good agreement between the calculated spectra and the measured one allows us to assign all observed resonances. The existence of pi* resonances in both the measured and the calculated OK-edge adsorption spectrum demonstrate that the delocalized pi-system of the thiophene part of the molecule is extended up to the oxygen atoms of the molecule.
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| 60. |
- Björneholm, O., et al.
(författare)
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Doppler splitting of in-flight auger decay of dissociating oxygen molecules : The localization of delocalized core holes
- 2000
-
Ingår i: Physical Review Letters. - : AMERICAN PHYSICAL SOC. - 0031-9007 .- 1079-7114. ; 84:13, s. 2826-2829
-
Tidskriftsartikel (refereegranskat)abstract
- By exploiting the core-excitation-induced dissociation of O-2, we find that the Auger emission exhibits a Doppler-like energy shift. We show this to be a manifestation of localization of the core hole and propose that the problem of core-hole localization versus delocalization in core-hole spectroscopies may be resolved by considering the nature of the measurement.
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