Thermodynamically Stable Cationic Dimers in Carboxyl-Functionalized Ionic Liquids: The Paradoxical Case of “Anti-Electrostatic” Hydrogen Bonding

We show that carboxyl-functionalized ionic liquids (ILs) form doubly hydrogen-bonded cationic dimers (c+=c+) despite the repulsive forces between ions of like charge and competing hydrogen bonds between cation and anion (c+–a−). This structural motif as known for formic acid, the archetype of double hydrogen bridges, is present in the solid state of the IL 1−(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC−CH2−py][NTf2]. By means of quantum chemical calculations, we explored different hydrogen-bonded isomers of neutral (HOOC–(CH2)n–py+)2(NTf2−)2, single-charged (HOOC–(CH2)n–py+)2(NTf2−), and double-charged (HOOC– (CH2)n−py+)2 complexes for demonstrating the paradoxical case of “anti-electrostatic” hydrogen bonding (AEHB) between ions of like charge. For the pure doubly hydrogen-bonded cationic dimers (HOOC– (CH2)n−py+)2, we report robust kinetic stability for n = 1–4. At n = 5, hydrogen bonding and dispersion fully compensate for the repulsive Coulomb forces between the cations, allowing for the quantification of the two equivalent hydrogen bonds and dispersion interaction in the order of 58.5 and 11 kJmol−1, respectively. For n = 6–8, we calculated negative free energies for temperatures below 47, 80, and 114 K, respectively. Quantum cluster equilibrium (QCE) theory predicts the equilibria between cationic monomers and dimers by considering the intermolecular interaction between the species, leading to thermodynamic stability at even higher temperatures. We rationalize the H-bond characteristics of the cationic dimers by the natural bond orbital (NBO) approach, emphasizing the strong correlation between NBO-based and spectroscopic descriptors, such as NMR chemical shifts and vibrational frequencies.

Asymptotic expansion of low-energy excitations for weakly interacting bosons

We consider a system of N bosons in the mean-field scaling regime for a class of interactions including the repulsive Coulomb potential. We derive an asymptotic expansion of the low-energy eigenstates and the corresponding energies, which provides corrections to Bogoliubov theory to any order in $1/N$ .

Hall viscosity and conductivity of two-dimensional chiral superconductors

We compute the Hall viscosity and conductivity of non-relativistic two-dimensional chiral superconductors, where fermions pair due to a short-range attractive potential, e.g. \boldsymbol{p+\mathrm{i}p}𝐩+i𝐩 pairing, and interact via a long-range repulsive Coulomb force. For a logarithmic Coulomb potential, the Hall viscosity tensor contains a contribution that is singular at low momentum, which encodes corrections to pressure induced by an external shear strain. Due to this contribution, the Hall viscosity cannot be extracted from the Hall conductivity in spite of Galilean symmetry. For mixed-dimensional chiral superconductors, where the Coulomb potential decays as inverse distance, we find an intermediate behavior between intrinsic two-dimensional superconductors and superfluids. These results are obtained by means of both effective and microscopic field theory.

Analytical solutions for three-dimensional Coulomb transition matrix at negative energy and integer values of interaction parameter

With the use of a stereographic projection of momentum space into a four-dimensional sphere of unit radius, the possibility of analytical solution of the three-dimensional two-body Lippmann–Schwinger equation with the Coulomb interaction at negative energy has been studied. Simple analytical expressions for the three-dimensional Coulomb transition matrix in the case of the repulsive Coulomb interaction and positive integer values of the Coulomb parameter have been obtained. The worked out method has also been applied to the generalized three-dimensional Coulomb transition matrix in the case of the attractive Coulomb interaction and negative integer values of the Coulomb parameter.

Strongly correlated superconductivity

We investigate the electronic properties of the ground state of strongly correlated electron systems. We use an optimization variational Monte Carlo method for the two-dimensional Hubbard model and the three-band d-p model. The many-body wavefunction is improved and optimized by introducing variational parameters that control the correlation between electrons. The on-site repulsive Coulomb interaction U induces strong antiferromagnetic (AF) correlation. There is a crossover from weakly to strongly correlated regions as U increases. We show an idea that high-temperature superconductivity occurs as a result of this crossover in the strongly correlated region where U is greater than the bandwidth.

Quantum Tunneling

Quantum tunneling, wherein a quanject has a non-zero probability of tunneling into and then exiting a barrier of finite width and height, is the subject of Chapter 13. The description for the one-dimensional case is extended to the barrier being inverted, which forms an attractive potential well. The first application of this analysis is to the emission of alpha particles from the decay of radioactive nuclei, where the alpha-nucleus attraction is modeled by a potential well and the barrier is the repulsive Coulomb potential. Excellent results are obtained. Ditto for the similar analysis of proton burning in stars and yet a different analysis that explains tunneling through a Josephson junction, the connector between two superconductors. The final application is to the scanning tunneling microscope, a device that allows the microscopic surfaces of solids to be mapped via electrons from the surface molecules tunneling into the tip of the STM probe.