Search arXivSearch

arXiv · 1703.07648

Magnetic field effects on dynamics of the ethylammonium nitrate ionic liquid confined between polar glass plates

Abstract

Self-diffusion and NMR relaxation of ethylammonium (EA) cations were studied in the protic ionic liquid ethylammonium nitrate (EAN) confined between parallel polar glass plates separated by a few um as a function of time after placement in a magnetic field of 9.40 T. Immediately after sample placement, the diffusion coefficient of EA (D) increased by a factor of 2, while the transverse NMR relaxation of NH3 protons decreased by factors of up to 22 in comparison with bulk EAN, according to previously published data. Further exposure to the magnetic field leads to gradual changes of D, T1 and T2 with a time constant of 70 min and a total equilibration time of longer than 4 hours. This process does not depend on the orientation of the glass plates relative to the magnetic field. Removing the sample from the magnetic field and repeating the experiment demonstrated that complete recovery of the sample to the accelerated D and shortened T2 occurs in approximately 24 hours. Thus, EA cation dynamics is accelerated relative to bulk when the cation is confined between polar glass plates and stored in the absence of a strong magnetic field, but demonstrate a trend to change to bulk values of D and T2 after exposure to a magnetic field. Because the observed characteristic times of the change far exceed molecular process times in EAN, we relate this phenomenon to reversible phase transformations occurring with EAN between polar plates outside the strong magnetic field, and reverse change of the phases after placing the sample in the magnetic field. This conclusion was confirmed by data of Raman spectroscopy.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Andrei Filippov. 2017-03-22. Magnetic field effects on dynamics of the ethylammonium nitrate ionic liquid confined between polar glass plates. https://doi.org/10.1039/c7cp06554j

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

Charge Transfer with a Spin. I: A Variational Constrained-CASSCF Framework for Investigating Charge Transfer in the Presence of Spin-Orbit Coupling

Charge transfer in open-shell molecular systems can involve a delicate interplay between charge localization, orbital relaxation, and spin-orbit coupling (SOC), particularly near ground-excited state crossings. Here, we introduce a very inexpensive variational framework for treating these effects in odd-electron systems by extending the electron/hole-transfer Dynamically-weighted State-Averaged Constrained CASSCF (eDSC/hDSC) method to include SOC. Our method incorporates the SOC Hamiltonian directly into the variational orbital optimization through complex-valued spinor orbitals, allowing orbital and spin degrees of freedom to relax self-consistently while preserving the time-reversal symmetry of doublet states. The method achieves smooth potential energy surfaces and rapid self-consistent field (SCF) convergence; moreover, from physically small to artificially large SOC strengths, the calculation can be converged to very tight thresholds across the whole potential energy surface. While the results presented here are for systems with two charge centers, as shown in the appendix, the theory is quite general and can be adapted to either a system of $N$ charge centers or a metal-molecule surface with a continuum of states, so that charge transport (and not just charge transfer) can also be studied. The approach therefore provides a route towards ab initio studies of spin-dependent charge transfer and charge transport in molecular systems with nontrivial spin degrees of freedom.

physics.chem-ph

Charge Transfer with a Spin. II: A Framework for Diabatization which Localizes Charge and Spin

We investigate a diabatization procedure that localizes charges (in real space) and localizes spins (in spin space) for open-shell systems that exhibit charge transfer in the presence of spin-orbit coupling. The procedure is applied to a two-state crossing between pairs of Kramers-restricted doublet states (which can also be considered effectively a four-state crossing). To generate the relevant diabatic states, we employ a two-step optimization over complex-unitary rotations that sequentially maximizes dipole and spin moments through iterative Jacobi sweeps; the resulting update rules are effectively equivalent to those of approximate joint diagonalization (AJD) applied to charge and spin. The method converges rapidly and yields smooth diabatic potential energy surfaces that preserve dipole and spin properties (e.g., a smoothly varying spin quantization axis) along the reaction coordinate while maintaining time-reversal symmetry.

physics.chem-ph

Fixed-Dimensional Latent Flow for Generating Variable-Size 3D Molecules

Molecular size is coupled to composition, structure, and function, yet most 3D molecular generators require a predefined atom count. We introduce Equivariant-Free Transformer-Autoencoded Latent Flow Matching, a two-stage framework that samples a fixed-dimensional latent vector using flow matching and uses an autoregressive Transformer to determine molecular size, atom types, coordinates, and chemical attributes. Canonical atom ordering and rigid-pose alignment enable Transformers without equivariant layers, while decoded attributes guide bond reconstruction. On PCQM4Mv2, unconditional generation yields 87.9\% unique, novel molecules passing sanitization and PoseBusters checks, exceeding baselines with lower end-to-end training and sampling time and higher end-to-end throughput. Across ten target HOMO-LUMO gaps, internal ranking retains 30\% of screened candidates and increases the density functional theory-verified hit rate within 0.1 eV from 25.0\% to 52.4\%, while largely preserving novelty and diversity. These results demonstrate fixed-dimensional latent generation with autoregressive decoding as a practical approach to molecular design without prespecifying size.

physics.chem-ph