It is shown that the asymmetric shape of lines in the electron paramagnetic resonance spectra of paramagnetic particle solutions caused by spin exchange in bimolecular particle collisions is due to the fact that, in the experiment, under the conditions of slow spin exchange, an absorption signal of nominally resonant spins and a "resonance" dispersion signal of nominally nonresonant spins with an abnormal phase of their quantum coherence are registered simultaneously. The mixing of these two signals is different for different resonance lines in the observed spectrum. A phenomenological model is proposed that can be used to find the phase of the "resonance" signal of non-resonant spins. The obtained results can be transferred to other systems to study the mechanisms of spectral diffusion, for example, chemical exchange by magnetic resonance methods.
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http://dx.doi.org/10.1021/acs.jpcb.0c04424 | DOI Listing |
Sci Rep
January 2025
Department of Applied Physics, School of Engineering Sciences, KTH Royal Institute of Technology, AlbaNova University Center, SE-10691, Stockholm, Sweden.
Non-trivial band topology along with magnetism leads to different novel quantum phases. When time-reversal symmetry is broken in three-dimensional topological insulators (TIs) through, e.g.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.
Density functional approximations can reduce the spin symmetry breaking observed for self-consistent field (SCF) solutions compared to Hartree-Fock theory, but the amount of exact Hartree-Fock (HF) exchange appears to be a key determinant in broken symmetry. To elucidate the precise role of exact exchange, we investigate the energy landscape of unrestricted Hartree-Fock and Kohn-Sham density functional theory for benzene and square cyclobutadiene, which provide paradigmatic examples of closed-shell and open-shell electronic structures, respectively. We find that increasing the amount of exact exchange leads to more local SCF minima, which can be characterized as combinatorial arrangements of unpaired electrons in the carbon π system.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry, Clemson University, Clemson, South Carolina 29634-0973, United States.
A new series of 222 adelite-type Co(GeO)(OH) ( = La-Sm) single crystals were grown by a high-temperature, high-pressure hydrothermal method (650 °C and 100 MPa). Single-crystal diffraction refinements yielded chiral one-dimensional (1D) chains of Co along the axis with an average 2.98 Å separation between Co centers in the [CoO(OH)] ribbon chains.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, United States.
Triplet-triplet energy transfer (TEnT) is of particular interest in various photochemical, photobiological, and energy science processes. It involves the exchange of spin and energy of electrons between two molecular fragments. Here, quasi-diabatic self-consistent field solutions were used to obtain the diabatic states involved in TEnT.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Lehrstuhl für Theoretische Chemie, Universität Erlangen-Nürnberg, Egerlandstr. 3, D-91058 Erlangen, Germany.
Methods based on density-functional theory usually treat open-shell atoms and molecules within the spin-unrestricted Kohn-Sham (KS) formalism, which breaks symmetries in real and spin space. Symmetry breaking is possible because the KS Hamiltonian operator does not need to exhibit the full symmetry of the physical Hamiltonian operator, but only the symmetry of the spin density, which is generally lower. Symmetry breaking leads to spin contamination and prevents a proper classification of the KS wave function with respect to the symmetries of the physical electron system.
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