Quantum-chemical study of 7Li NMR shifts in the context of delithiation of paramagnetic lithium vanadium phosphate, Li3V2(PO4)3 (LVP).

The lithium NMR shifts of three paramagnetic materials important in the charging/discharging processes of lithium vanadium phosphate cathode materials have been studied by large-scale quantum-chemical methodology. Namely, the 7Li NMR shifts of the fully lithiated Li3V2(PO4)3 (LVP3.0), and of the partly delithiated Li2.5V2(PO4)3 (LVP2.5) and Li2V2(PO4)3 (LVP2.0), have been computed and analyzed using a recently proposed approach (A. Mondal, M. Kaupp J. Phys. Chem. C 123 (2019) 8387-8405) that accounts for the Fermi-contact, pseudo-contact, as well as orbital shifts, combining periodic computations with an incremental cluster model. LVP3.0 and LVP2.0 exhibit three and two unique Li sites, respectively, which could be assigned to their experimental 7Li NMR signals. In case of LVP2.0, the computations clearly assigned the signals at 143 ppm and 77 ppm to the Li(1) and Li(2) sites, respectively, even though the latter is connected to Vb(+III d2 sites and the former to Va(+IV) d1 sites. LVP2.5 is the most complex of these three materials, exhibiting a 50% occupation of Li(3) sites, which generates much more complicated Li NMR spectra with seven peaks that partly are closely spaced. Exploring three different occupation patterns, the computations can clearly assign five of the seven signals to one type of Li site and give most probable assignments for the two remaining signals. Notably, the calculations support seven signals to be assigned to LVP2.5, while previous interpretations took two of the signals as being entirely due to contamination by LVP2.0. The accuracy of the computations could probably be improved further by full DFT optimization of large super-cell structures. This work suggests that first-principles computations of NMR shifts of extended paramagnetic solids provide an important tool for the analysis of even rather complex NMR spectra.

Quantum-Chemical Approach to NMR Chemical Shifts in Paramagnetic Solids Applied to LiFePO4 and LiCoPO4.

A novel protocol to compute and analyze NMR chemical shifts for extended paramagnetic solids, accounting comprehensively for Fermi-contact (FC), pseudocontact (PC), and orbital shifts, is reported and applied to the important lithium ion battery cathode materials LiFePO4 and LiCoPO4. Using an EPR-parameter-based ansatz, the approach combines periodic (hybrid) DFT computation of hyperfine and orbital-shielding tensors with an incremental cluster model for g- and zero-field-splitting (ZFS) D-tensors. The cluster model allows the use of advanced multireference wave function methods (such as CASSCF or NEVPT2). Application of this protocol shows that the 7Li shifts in the high-voltage cathode material LiCoPO4 are dominated by spin-orbit-induced PC contributions, in contrast with previous assumptions, fundamentally changing interpretations of the shifts in terms of covalency. PC contributions are smaller for the 7Li shifts of the related LiFePO4, where FC and orbital shifts dominate. The 31P shifts of both materials finally are almost pure FC shifts. Nevertheless, large ZFS contributions can give rise to non-Curie temperature dependences for both 7Li and 31P shifts.

Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study.

Understanding host-guest interactions is one of the key requirements for adjusting properties in metal-organic frameworks (MOFs). In particular, systems with coordinatively unsaturated Lewis acidic metal sites feature highly selective adsorption processes. This is attributed to strong interactions with Lewis basic guest molecules. Here we show that a combination of 13C MAS NMR spectroscopy with state-of-the-art density functional theory (DFT) calculations allows one to unravel the interactions of water, 2-aminopyridine, 3-aminopyridine, and diethylamine with the open metal sites in Cr-MIL-101. The 13C MAS NMR spectra, obtained with ultrafast magic-angle spinning, are well resolved, with resonances distributed over 1000 ppm. They present a clear signature for each guest at the open metal sites. Based on competition experiments this leads to the following binding preference: water < diethylamine ≈ 2-aminopyridine < 3-aminopyridine. Assignments were done by exploiting distance sum relations derived from spin-lattice relaxation data and 13C{1H} REDOR spectral editing. The experimental data were used to validate NMR shifts computed for the Cr-MIL-101 derivatives, which contain Cr3O clusters with magnetically coupled metal centers. While both approaches provide an unequivocal assignment and the arrangement of the guests at the open metal sites, the NMR data offer additional information about the guest and framework dynamics. We expect that our strategy has the potential for probing the binding situation of adsorbate mixtures at the open metal sites of MOFs in general and thus accesses the microscopic interaction mechanisms for this important material class, which is essential for deriving structure-property relationships.

Large-Scale Computation of Nuclear Magnetic Resonance Shifts for Paramagnetic Solids Using CP2K.

Large-scale computations of nuclear magnetic resonance (NMR) shifts for extended paramagnetic solids (pNMR) are reported using the highly efficient Gaussian-augmented plane-wave implementation of the CP2K code. Combining hyperfine couplings obtained with hybrid functionals with g-tensors and orbital shieldings computed using gradient-corrected functionals, contact, pseudocontact, and orbital-shift contributions to pNMR shifts are accessible. Due to the efficient and highly parallel performance of CP2K, a wide variety of materials with large unit cells can be studied with extended Gaussian basis sets. Validation of various approaches for the different contributions to pNMR shifts is done first for molecules in a large supercell in comparison with typical quantum-chemical codes. This is then extended to a detailed study of g-tensors for extended solid transition-metal fluorides and for a series of complex lithium vanadium phosphates. Finally, lithium pNMR shifts are computed for Li3V2(PO4)3, for which detailed experimental data are available. This has allowed an in-depth study of different approaches (e.g., full periodic versus incremental cluster computations of g-tensors and different functionals and basis sets for hyperfine computations) as well as a thorough analysis of the different contributions to the pNMR shifts. This study paves the way for a more-widespread computational treatment of NMR shifts for paramagnetic materials.

Supramolecular polyelectrolyte complex (SPEC): pH dependent phase transition and exploitation of its carrier properties.

A supramolecular poly-electrolyte complex (SPEC) comprising poly-electrolyte acrylic acid with supramolecularly complexed guanidium is reported. This complex shows pH responsive phase transitions, which are described and characterized using microscopy, spectroscopy, density functional theory studies and Monte Carlo simulations. The phase behaviour of the SPEC is exploited by loading a dye like perylene and a drug, viz., doxorubicin, and their pH dependent controlled release is demonstrated, owing to the pH dependent phase change of the SPEC.

Thermal lattice expansion effect on reactive scattering of H2 from Cu(111) at T(s) = 925 K.

Surface phonons and surface temperature may have important effects on reactions of molecules at surfaces, and at present much remains unknown about these effects. A question addressed here, which has received little attention so far, is how reaction at elevated temperature is affected by thermal lattice expansion. To answer this question for the benchmark reaction of H2 and D2 with Cu(111), we have performed quantum and quasi-classical dynamics calculations. The specific reaction parameter (SRP) approach to density functional theory (DFT) has been used to compute the required six-dimensional potential energy surfaces (PES). Computed reaction probabilities and rotational quadrupole alignment parameters have been compared for surface temperatures Ts = 0 and 925 K. Surface thermal expansion of the lattice leads to a considerable decrease of reaction barrier heights and thereby to increased reaction probabilities as well as decreased rotational quadrupole alignment parameter values in associative desorption.

Water dissociation on Cu(111): effects of molecular orientation, rotation, and vibration on reactivity.

Three-dimensional time-dependent quantum mechanical method has been used to study the influence of orientation, rotation, and vibration on the dissociation of water molecule on Cu(111) surface, using London-Eyring-Polanyi-Sato potential energy surface. Our calculations show that dependency of dissociation probability on the initial orientation of the molecule changes with the vibrational state of the molecule. It has also been found that for v(0) = 0 and 1, where v(0) stands for the vibrational state of the pseudo diatomic HO-H, the rotational excitation of the molecule increases the reactivity, whereas for v(0) = 2, the rotational excitation of the molecule decreases the reactivity. Vibrational excitation of the molecule greatly enhances the dissociation probability.

Unique emission from norbornene derived terpyridine--a selective chemodosimeter for G-type nerve agent surrogates.

A new chemodosimeter for a G-type agent that exploits norbornene derived terpyridine (NDT)-lanthanide unique emission is reported. The unusual emission between terpyridine and norbornene motifs of NDT is attributed to the significant difference in the position of the HOMO and LUMO wave functions that prevents the non-radiative relaxation pathway. An interesting magenta emission from NDT along with Eu(III) is utilized as a new fluorometric chemodosimeter that selectively detects (by changing the observed magenta emission to blue) G-type agent surrogates. A detection limit of 40 ppb is obtained and the selectivity for reactive surrogates over a variety of other close chemical analogs is demonstrated.