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A reversible photoinduced intramolecular crankshaft-type rearrangement in a glycoconjugate proceeds simultaneously at both the –N–N and CH–C– bonds.

High-resolution NMR experiments revealed that differently substituted quinazolinone-based Schiff bases undergo anti to syn isomerisation on exposure to ultraviolet light in DMSO solution.

A new approach to assessing the effect of the transmission of spin-polarization by π-orbitals (π-TSP) is presented. In order to switch off the π-TSP effect, we artificially average the α- and β-densities of the valence π-orbitals when calculating the exchange-correlation contribution to the Fock matrix in the unrestricted Kohn-Sham framework. The π-TSP effect is then evaluated as the difference between the results obtained with switched-on and switched-off options. This approach is applied to estimate the π-TSP effect on the Fermi-contact contribution to spin-spin couplings and EPR hyperfine structure coupling constants. The π-TSP effect on the distribution of spin-density, spin-spin coupling pathways and pathways of EPR hyperfine couplings is demonstrated for benzene, naphthalene, 1,3,5,7,9-decapentaene and the 1,3,5,7,9-decapentaen-1-yl radical. The sign alternation of the spin-polarization transmitted by π-orbitals is explained in a theoretical framework based on perturbation theory. However, the delocalized nature of the π-system can interfere with the sign alternation in certain cases, two of which - the cyclobutadiene dication and the cyclooctatetraene dication - are examined, and an explanation for which is provided.

EPR and NMR experiments on a quinazolinone-based Schiff's base in DMSO solution showed that irradiation with UV light (365 nm) leads to photochemically-induced isomerization from the anti- to the higher-energy syn-form around the –N–N linkage. The anti- to syn-isomerization was relatively fast, and the maximum amount of conversion detected (25%) was reached within 10 min; thermodynamic equilibrium re-established itself in about 15 min. DFT calculations were performed on the investigated compound and small model systems, and reproduced the experimental fact of the anti-conformer being lower in energy than the syn. Theoretical analysis of excited states, including visualisation of natural transition orbitals, identified possible pathways for syn–anti isomerisation, although the details vary with π-system size, making the use of small models of limited utility. The investigated compound probably isomerises through the third singlet excited state (S3), a π–π* excitation, relaxing through S2, also a π–π* state.

At the 4-component level of theory, the EPR g-tensor is a first-order property, i.e. each component of the g-tensor is an expectation value. This makes visualization of the g-tensor in terms of 3-dimensional real-space functions straightforward. These functions can be considered as ‘g-value densities’, and be plotted to give a 3-dimensional visualization of the g-tensor. This can be decomposed further into terms corresponding to different operators in the g-tensor calculation. Initial results of the visualization of the g-value density are presented, including of changes caused by H-bonding. This new approach expands existing techniques for analysis of factors affecting the g-tensor.

This manuscript describes new phenomena that currently are not taken into account in both experimental EPR spectra interpretations and quantum chemical calculations of EPR parameters. This article presents an argument, with evidence, against the common belief that in the absence of an external magnetic field the total energy of a doublet system is independent of the spin orientation. Consequences of this phenomenon for interpretation of EPR experimental studies as well as for quantum chemical calculations of EPR parameters are discussed.

Car-Parrinello molecular dynamics (CPMD) simulations have been performed on ubisemiquinone radical anion in aqueous solution. The different types of hydrogen bonding formed between the semiquinone and the solvent were studied in terms of frequency and directionality, in comparison with the parent benzosemiquinone radical anion. The EPR parameters (g-tensors and hyperfine coupling constants) were obtained from quantum chemical property calculations performed on snapshots along the MD trajectory, and the contributions of different solvation effects to the EPR parameters have been evaluated. The influence of the anion’s conformational behaviour was examined, including the orientation-dependent effects of hyperconjugation on side-chain hyperfine coupling.

Car-Parrinello molecular dynamics simulations of benzoquinone and benzosemiquinone radical anion in both aqueous solution and the gas phase have been carried out at ambient conditions. Hydrogen bonding is considerably more extensive to the anionic than to the neutral aqueous system. In addition to the conventional hydrogen bonding to the carbonyl oxygen atoms, T-stacked hydrogen bonding to the π-system is statistically and energetically significant for the semiquinone anion but not for the neutral quinone. EPR g-tensors have been calculated at DFT level for snapshots taken at regular intervals from the gas-phase and solution semiquinone anion trajectories. Different criteria for extraction of semiquinone/water clusters from the solution trajectory give insight into the effects of different interactions on the g-tensor, as does correlation of the g-tensor with statistically significant hydrogen-bond configurations identified along the trajectories. Comparison of gas-phase and solution results indicates opposite directions of direct electronic and indirect structural influences of hydrogen bonding on g-tensors. Short-time oscillations in gx along the trajectory are due mainly to CO bond vibrations. Copyright © 2005 John Wiley & Sons, Ltd.

Car-Parrinello molecular dynamics (CP-MD) simulations of the benzosemiquinone radical anion in aqueous solution have been performed at ambient conditions. Analysis of the trajectory shows not only extensive hydrogen bonding to the carbonyl oxygen atoms (ca. 4-5.6 water molecules depending on distance criteria), but also relatively long-lived "T-stacked" hydrogen bonds to the semiquinone pi-system. These results are discussed in the context of recent findings on semiquinone-protein interactions in photosynthetic reaction centers, and of EPR and vibration spectroscopical data for the aqueous system. Snapshots from the CP-MD trajectory are used for the first quantum chemical analyses of dynamical effects on electronic g-tensors, using cluster models and a recently developed density functional method. In particular, the effects of intermolecular hydrogen-bond dynamics on the g-tensor components are examined, in comparison with recent EPR and ENDOR studies.

In a recent EPR study, Gross et al. (B. Gross, H. Dilger, R. Scheuermann, M. Pach and E. Roduner, J. Phys. Chem. A, 2001, 105, 10012) found that hydrogen atoms trapped in silasesquioxanes unexpectedly exhibit g-values significantly larger than the free-electron value, with an appreciable dependence on the external substituents of the cage. Here it is shown by density functional calculations and detailed analyses of the g-values that (a) the positive g-shifts are predominantly due to spin–orbit coupling from the cage oxygen atoms; (b) in second-order perturbation theory the g-shifts arise mainly from couplings of t1g oxygen-based cage orbitals to the a1g singly occupied molecular orbital, and (c) the reduction of the g-shifts by external substituents is mainly caused by lower spin density on the cage oxygen atoms, due in part to reduced delocalization of the singly occupied MO onto the cage. Calculations with the hydrogen atom displaced from the center of the cage provide explanations for the negligible temperature dependence of the g-values compared to an experimentally notable dependence of the hyperfine couplings. Large direct halogen spin–orbit contributions and negative g-shifts are predicted for systems with heavy halogen atoms as external substituents. Comparison of different exchange-correlation functionals, and of spin-restricted and -unrestricted calculations reveals unexpected trends for spin density distribution and g-values: Spin polarization increases the computed g-shifts, whereas the admixture of Hartree–Fock exchange in hybrid functionals decreases them.

NMR spin-spin couplings through a hydrogen bond in the free-base and protonated forms of the complete series of [(15)N2]-N-methylated 1,8-diaminonaphthalenes have been analyzed using quantum chemistry tools. The dominating role of the overlap of the coupling pathway orbitals has been demonstrated. The correlation of the sum of the (13)C NMR shifts of the naphthalene ring C(1,8) carbons directly attached to the interacting nitrogens with the J(N-N) values and the degree of methylation found earlier by G. C. Lloyd-Jones et al. [Chem.-Eur. J. 2003, 9, 4523] have been reexamined. It has been found that the correlations of J(N-N) and [ΔΣC(1,8)] with the degree of methylation have different reasons. While the former is mostly connected with the structural changes due to the solvent effect, the latter is attributed to the changes in the paramagnetic contributions from the C-N and C-C bonds caused by the replacement of a hydrogen by a methyl group.

Based on Car-Parrinello ab initio molecular dynamics simulations of the benzosemiquinone radical anion in both aqueous solution and the gas phase, density functional calculations provide the currently most refined EPR hyperfine coupling (HFC) tensors of semiquinone nuclei and solvent protons. For snapshots taken at regular intervals from the molecular dynamics trajectories, cluster models with different criteria for inclusion of water molecules and an additional continuum solvent model are used to analyse the HFCs. These models provide a detailed picture of the effects of dynamics and of different intermolecular interactions on the spin-density distribution and HFC tensors. Comparison with static calculations allows an assessment of the importance of dynamical effects, and of error compensation in static DFT calculations. Solvent proton HFCs depend characteristically on the position relative to the semiquinone radical anion. A point-dipolar model works well for in-plane hydrogen-bonded protons but deviates from the quantum chemical values for out-of-plane hydrogen bonding.

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich., This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively., The calculation of the g tensor of the main +NH3–˙CH–COO− radiation-induced radical in solid-state α-glycine presents a real challenge to computational methods. Density functional calculations of this spectroscopic property struggle with its small anisotropy and the zwitterionic nature of the amino acids in the crystal of this seemingly simple system. Here, several factors influencing the calculated g tensor are examined by comparing with experimental data. The extent of the molecular environment is varied in both a cluster and a periodic approach and dynamic calculations are performed to account for temperature effects. The latter does not necessarily lead to a better agreement with experiment than a static calculation. Application of a periodic approach is straightforward, but an all-electron scheme clearly is favorable. In a cluster approach, the selected basis set and density functional are of less importance, provided a hybrid functional is used to prevent cluster boundary effects. The applied spin–orbit coupling operators and proper treatment of the gauge origin of the magnetic vector potential also seem to be less critical than in other, similar molecular systems. But a careful selection of the cluster size proves to be essential for this glycine radical system. The calculated g tensor varies significantly with increasing cluster size, yielding only a good agreement with experiment when 5–7 glycine molecules in the immediate environment of the central glycine radical are incorporated. Further expansion of the cluster size can even lead to an essentially incorrect description of the radical in the condensed phase, indicating that bigger clusters can become unbalanced.