Molecular chirality plays a crucial role in physics, chemistry, life sciences and pharmacology. Nowadays, the chiral discrimination and control at the single-molecule level is urgently needed to reveal the origin of the chirality-relevant phenomena by recovering the information disturbed by the ensemble averaging. The method of magnetic resonance (MR), as one of powerful tools for structure analysis, is blind to the molecular chirality in the absence of a chiral reagent. Here we propose and experimentally demonstrate a direct MR-based method for determining the chirality at the single-molecule level through constructing the symmetry-breaking dynamics of nearby nuclear spins. In principle, the mirror asymmetry of two enantiomers in real space is manifested by breaking the joint symmetry of the mirror reflection and time reversal in spin space under spin dynamics. Experimentally, two enantiomers are indistinguishable from the dynamics of strongly-coupled but unpolarized nuclear spins, but diverge evidently in the dynamical results that break the field-inversion symmetry after spins are polarized. Our method and results will benefit the study of chirality-induced properties in the fields of chemistry and biology.
Molecular chirality plays a crucial role in physics, chemistry, life sciences and pharmacology. Nowadays, the chiral discrimination and control at the single-molecule level is urgently needed to reveal the origin of the chirality-relevant phenomena by recovering the information disturbed by the ensemble averaging. The method of magnetic resonance (MR), as one of powerful tools for structure analysis, is blind to the molecular chirality in the absence of a chiral reagent. Here we propose and experimentally demonstrate a direct MR-based method for determining the chirality at the single-molecule level through constructing the symmetry-breaking dynamics of nearby nuclear spins. In principle, the mirror asymmetry of two enantiomers in real space is manifested by breaking the joint symmetry of the mirror reflection and time reversal in spin space under spin dynamics. Experimentally, two enantiomers are indistinguishable from the dynamics of strongly-coupled but unpolarized nuclear spins, but diverge evidently in the dynamical results that break the field-inversion symmetry after spins are polarized. Our method and results will benefit the study of chirality-induced properties in the fields of chemistry and biology.
Achiral molecules can be prepared in superposition states that are chiral. Here, we propose angular momentum orientation in the molecular frame to achieve the required symmetry breaking, exerting rotational control without the need for laboratory frame orientation. We derive the conditions for chiral rotational dynamics from the requirement to simultaneously break the continuous spatial rotational symmetry and the molecular point group symmetry. This can be achieved by three microwave pulses as well as two non-resonant optical pulses in combination with a THz pulse or three THz pulses, all with mutually orthogonal polarization directions, and the ensuing dynamics can be probed by photoelectron circular dichroism. Our results open the way for distinguishing structural from dynamical enantioselectivity and investigating time-odd chiroptical phenomena in randomly oriented molecules.
The optical bistability (OB) and multistability (OM) in chiral molecules are investigated by placing the sample into a unidirectional ring cavity. Because of broken mirror symmetry of the effective potential, the chiral molecules have a cyclic three-level Δ-configuration structure, in which one- and two-photon transitions can coexist. We find that the OB is achievable in this system on exact one-, two- and three-photon resonance conditions but absent in the three-level Λ-type system under the two-photon resonance. Moreover, the OM and the switching between OB and OM are also realized by choosing parameters properly. Interestingly, the left- and right-handed chiral molecules exhibit different bistable and multistable behaviors. It is shown that the threshold intensity of OB is strongly dependent on the percentage of the two enantiomers in the mixture. This provides an effective approach to probe molecular chirality and to determine enantiomer excess, which may find potential application in organic chemistry, pharmacology, biochemistry, etc..
Molecular magnets are ideal systems to probe the realm that borders quantum and classical physics, as well as to study decoherence phenomena in nanoscale systems. The control of the quantum behavior of these materials and their structural characteristics requires synthesis of new complexes with desirable properties which will allow probing of the fundamental aspects of nanoscale physics and quantum information processing. Of particular interest among the magnetic molecular materials are single-molecule magnets (SMMs) and antiferromagnetic (AFM) molecular wheels in which the spin state of the molecule is known to behave quantum mechanically at low temperatures. In previous experiments the dynamics of the magnetic moment of the molecules is governed by incoherent quantum tunneling. Short decoherence times are mainly due to interactions between molecular magnets within the crystal and interactions of the electronic spin with the nuclear spin of neighboring ions within the molecule. This decoherence problem has imposed a limit to the understanding of the molecular spin dynamics and the sources of decoherence in condensed matter systems. Particularly, intermolecular dipolar interactions within the crystal, which shorten the coherence times in concentrated samples, have stymied progress in this direction. Several recent works have reported a direct measurement of the decoherence time in molecular magnets. This has been done by eliminating the dephasing created by dipolar interactions between neighboring molecules. This has been achieved by a) a dilution of the molecules in a liquid solution to decrease the dipolar interaction by separating the molecules, and b) by polarizing the spin bath by applying a high magnetic field at low temperatures. Unfortunately, both approaches restrict the experimental studies of quantum dynamics. For example, the dilution of molecular magnets in liquid solution causes a dispersion of the molecular spin orientation and anisotropy axes, while the large fields required to polarize the spin bath overcome the anisotropy of the molecular spin. In this thesis I have explored two methods to overcome dipolar interactions in molecular magnets: a) studying the dynamics of molecular magnets in single crystals where the separation between magnetic molecules is obtained by chemical doping or where the high crystalline quality allows observations intrinsic to the quantum mechanical nature of the tunneling of the spin, and b) studying the electronic transport through an individual magnetic molecule which has been carefully placed in a single-electron transistor device. I have used EPR microstrip resonators to measure Fe17Ga molecular wheels within single crystals of Fe18 AFM wheels, as well as demonstrating, for the first time in a Single Molecule Magnet, the complete suppression of a Quantum Tunneling of the Magnetization transition forbidden by molecular symmetry.
Chiral discrimination that is efficient at detecting tiny amounts of chiral substances, especially at the single-molecule level, is in great demand. Here, we propose a single-shot nondestructive quantum sensing method addressing such an issue. Our scheme consists of two steps. In the first step, the two enantiomers are prepared in different rotational states via microwave enantio-specific state transfer. Then, chiral discrimination is transferred to quantum hypothesis testing. In the second step, we for the first time introduce a nondestructive quantum-state detection technique assisted with a microwave resonator for chiral discrimination, through which the molecular chirality is determined by the sign of the output signals. Using a typical chiral molecule, 1,2-propanediol, and an experimentally feasible model based on spherical Fabry–Pérot cavity, we show that the molecular chirality of slowly moving enantiopure gaseous samples with 10 2 –10 3 molecules can be highly credibly distinguished in a single-shot detection. By further trapping chiral molecules, it is promising to achieve chiral discrimination at the single-molecule level by using our approach.
Two molecules are enantiomers if they are nonsuperimposable mirror images of each other. Electric dipole-allowed cyclic transitions |1⟩ → |2⟩ → |3⟩ → |1⟩ obey the symmetry relation O R = − O S, where O R, S = (μ 21 R, S E 21 )(μ 13 R, S E 13 )(μ 32 R, S E 32 ) and R and S label the two enantiomers. Herein, we generalize the concept of topological frequency conversion to an ensemble of enantiomers. We show that, within a rotating-frame, the pumping power between fields of frequency ω 1 and ω 2 is sensitive to enantiomeric excess, P 2 → 1 = ℏ[ω 1 ω 2 C L R /(2π)]( N R – N S ), where N i is the number of enantiomers i and C L R is an enantiomer-dependent Chern number. Connections with chiroptical microwave spectroscopy are made. Our work provides an underexplored and fertile connection between topological physics and molecular chirality.
We propose a robust platform for simulating chiral quantum magnetism using linear arrays of trapped asymmetric top molecules, specifically 1,2-propanediol (C3H8O2). By mapping the Stark-dressed rotational states onto an effective spin-1/2 subspace, we rigorously derive a generalized XXZ Heisenberg Hamiltonian governing the underlying many-body dynamics. Unlike standard solid-state models where the topological Dzyaloshinskii-Moriya Interaction (DMI) is introduced phenomenologically, we demonstrate that DMI emerges \textit{ab initio} from the molecular stereochemistry. Specifically, the interference between the transition dipole moments of heterochiral enantiomer pairs (L-R), which breaks inversion symmetry, generates a tunable DMI that stabilizes a Chiral Luttinger Liquid phase. Through a comprehensive phase-diagram analysis, we identify an optimal experimental regime characterized by intermolecular separations of r≈1.5nm and intermediate electric-field strengths dε/B≈2.5. In this window, the system is protected from trivial field-polarized phases and exhibits a robust gapless spin-spiral texture. Our results establish 1,2-propanediol arrays as a versatile quantum simulator, providing a direct microscopic link between molecular chirality and topological many-body phases.