Electric control of spin states in frustrated triangular molecular magnets

Frustrated triangular molecular magnets are a very important class of magnetic molecules since the absence of inversion symmetry allows an external electric field to couple directly with the spin chirality that characterizes their ground state. The spin-electric coupling in these molecular magnets leads to an efficient and fast method of manipulating spin states, making them an exciting candidate for quantum information processing. The efficiency of the spin-electric coupling depends on the electric dipole coupling between the chiral ground states of these molecules. In this paper, we report on first-principles calculations of spin-electric coupling in $\{V_3\}$ triangular magnetic molecule. We have explicitly calculated the spin-induced charge redistribution within the magnetic centers that is responsible for the spin-electric coupling. Furthermore, we have generalized the method of calculating the strength of the spin-electric coupling to calculate any triangular spin 1/2 molecule with $C_3$ symmetry and have applied it to calculate the coupling strength in $\{V_{15}\}$ molecular magnets

Transition from a polaronic condensate to a degenerate Fermi gas of heteronuclear molecules

The interplay of quantum statistics and interactions in atomic Bose--Fermi mixtures leads to a phase diagram markedly different from pure fermionic or bosonic systems. However, investigating this phase diagram remains challenging when bosons condense. Here, we observe evidence for a quantum phase transition from a polaronic to a molecular phase in a density-matched degenerate Bose--Fermi mixture. The condensate fraction, representing the order parameter of the transition, is depleted by interactions and the build-up of strong correlations results in the emergence of a molecular Fermi gas. By driving through the transition, we ultimately produce a quantum-degenerate sample of sodium-potassium molecules exhibiting a large molecule-frame dipole moment of 2.7 Debye. The observed phase transition represents a new phenomenon complementary to the paradigmatic BEC-BCS crossover observed in Fermi systems.Comment: 12 pages, 9 figure

Frozen natural orbitals for the state-averaged driven similarity renormalization group

We present a reduced-cost implementation of the state-averaged driven similarity renormalization group (SA-DSRG) based on the frozen natural orbital (FNO) approach. The natural orbitals (NOs) are obtained by diagonalizing the one-body reduced density matrix from SA-DSRG second-order perturbation theory (SA-DSRG-PT2). Subsequently, the virtual NOs with occupation numbers (ONs) smaller than a user-defined threshold are excluded from the high-level electron correlation treatment beyond SA-DSRG-PT2. An additive second-order correction is applied to the SA-DSRG Hamiltonian to reintroduce the correlation effect from the discarded orbitals. The FNO SA-DSRG method is benchmarked on 35 small organic molecules in the QUEST database. When keeping 98-99% of the cumulative ONs, the mean absolute error in the vertical transition energies due to FNO is less than 0.01 eV. Using the same FNO threshold, we observe a speedup of 9 times the conventional SA-DSRG implementation for nickel carbonyl with a quadruple-$\zeta$ basis set. The FNO approach enables third-order SA-DSRG perturbation theory computations on chloroiron corrole [FeCl(C$_{19}$H$_{11}$N$_4$)] with more than 1000 basis functions

Integrated energy storage and CO2 conversion using an aqueous battery with tamed asymmetric reactions

Developing a CO2-utilization and energy-storage integrated system possesses great advantages for carbon- and energy-intensive industries. Efforts have been made to developing the Zn-CO2 batteries, but access to long cycling life and low charging voltage remains a grand challenge. Here we unambiguously show such inefficiencies originate from the high-barrier oxygen evolution reaction on charge, and by recharging the battery via oxidation of reducing molecules, Faradaic efficiency-enhanced CO2 reduction and low-overpotential battery regeneration can be simultaneously achieved. Showcased by using hydrazine oxidation, our battery demonstrates a long life over 1000 hours with a charging voltage as low as 1.2 V. The low charging voltage and formation of gaseous product upon hydrazine oxidation are the key to stabilize the catalyst over cycling. Our findings suggest that by fundamentally taming the asymmetric reactions, aqueous batteries are viable tools to achieve integrated energy storage and CO2 conversion that is economical, highly energy efficient, and scalable

Cold polar molecules in bilayers

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Quantum Monte Carlo calculations of energy gaps from first principles

We review the use of continuum quantum Monte Carlo (QMC) methods for the calculation of energy gaps from first principles, and present a broad set of excited-state calculations carried out with the variational and fixed-node diffusion QMC methods on atoms, molecules, and solids. We propose a finite-size-error correction scheme for bulk energy gaps calculated in finite cells subject to periodic boundary conditions. We show that finite-size effects are qualitatively different in two-dimensional materials, demonstrating the effect in a QMC calculation of the band gap and exciton binding energy of monolayer phosphorene. We investigate the fixed-node errors in diffusion Monte Carlo gaps evaluated with Slater-Jastrow trial wave functions by examining the effects of backflow transformations, and also by considering the formation of restricted multideterminant expansions for excited-state wave functions. For several molecules, we examine the importance of structural relaxation in the excited state in determining excited-state energies. We study the feasibility of using variational Monte Carlo with backflow correlations to obtain accurate excited-state energies at reduced computational cost, finding that this approach can be valid. We find that diffusion Monte Carlo gap calculations can be performed with much larger time steps than are typically required to converge the total energy, at significantly diminished computational expense, but that in order to alleviate fixed-node errors in calculations on solids the inclusion of backflow correlations is sometimes necessary

Efimov Physics in a three-component Fermi gas

This thesis reports on experiments studying the few-body physics of three distinguishable fermionic atoms with large scattering lengths. The experiments were performed with ultracold gases of fermionic 6Li atoms in three different hyperfine states. By tuning the strength of the interactions between the atoms with Feshbach resonances and measuring the rate constants for inelastic three-atom and atom-dimer collisions the intersections of two universal trimer states with the three-atom and atom-dimer continuum could be located. Subsequently, one of these Efimov states was directly observed with RF-association spectroscopy. Using this technique the binding energy of this Efimov state was measured as a function of the strength of the interparticle interactions. The experiments presented in this thesis provide a nearly complete understanding of the universal few-body physics of three-component Fermi gases of 6Li atoms. This understanding will be the foundation for future studies of the many-body physics of three-component Fermi gases