Philip Caesar M. Flores

Photoelectron circular dichroism (PECD) manifests as a forward-backward asymmetry of electron emission in the direction orthogonal to the light polarization plane via one-photon ionization of chiral molecules with circularly polarized light. Multi-polar ‘PECD’ currents, i.e., currents resolved along multiple directions, have also been predicted using two mutually-orthogonal linearly polarized light with carrier frequencies ω and 2ω. These currents arise from the interference between the one- and two-photon transitions. Here, we will show that photoelectron spin detection reveals enantio-sensitive multi-polar currents already in the one-photon regime since the two axes can be marked by the photoelectron momentum and spin-detection axis. Specifically, we consider one-photon ionization of an isotropic ensemble of randomly oriented chiral molecules via circularly polarized light and show that the resulting spin-resolved current has three components whose magnitudes are comparable and can be larger than PECD: (i) a spin-polarization vortex in the plane of light polarization that rotates in opposite directions for opposite enantiomers, (ii) either a spin-sink or source in the plane of light polarization for opposite enantiomers, and (iii) a spin analog of photoelectron vortex dichroism wherein the detected photoelectron spin encodes molecular chirality.

Chirality describes the asymmetry between an object and its mirror image and manifests itself in diverse functionalities across all scales of matter - from molecules and aggregates to thin films and bulk chiral materials. A particularly intriguing example is chirality-induced spin selectivity (CISS), where chiral structures orient electron spins enantio-sensitively. Despite extensive research, the fundamental origin of spin-chirality coupling, the unexpectedly large magnitude of the CISS effect, and the possible role of electromagnetic fields in it remain unclear. Here, we address these issues by examining the simplest scenario: spin-resolved photoionization of randomly oriented chiral molecules. We uncover a universal mechanism of spin-selective chiral photodynamics, arising solely from electric-dipole interactions and previously unrecognized. This mechanism embodies a chiral molecular compass - a photoinduced magnetization vector that orients the photoelectron spin. It arises in photoexcited chiral molecules even under isotropic illumination, operates even in isotropic chiral media, and enables a phenomenon central to CISS: locking of the photoelectron spin orientation to molecular geometry. It shows that chiral molecules can sustain time-odd correlations whereas achiral molecules cannot. Our findings have broad implications, from unambiguously identifying the origin of CISS effect in photoionization to harvesting correlations underlying this effect in other forms of CISS in various chiral materials.

It has been shown in Phys. Rev. Lett., 108 170402 (2012), that quantum tunneling is instantaneous using a time-of-arrival (TOA) operator constructed by Weyl quantization of the classical TOA. However, there are infinitely many possible quantum images of the classical TOA, leaving it unclear if one is uniquely preferred over the others. This raises the question on whether instantaneous tunneling time is simply an artifact of the chosen ordering rule. Here, we demonstrate that tunneling time vanishes for all possible quantum images of the classical arrival time, irrespective of the ordering rule between the position and momentum observables. The result still holds for TOA-operators that are constructed independent of canonical quantization, while still imposing the correct algebra defined by the time-energy canonical commutation relation.

We introduce the concept of partial-tunneling and full-tunneling processes to explain the seemingly contradictory non-zero and vanishing tunneling times often reported in the literature. Our analysis starts by considering the traversal time of a quantum particle through a potential barrier, including both above- and below-barrier traversals, using the theory of time-of-arrival operators. We then show that there are three traversal processes corresponding to non-tunneling, full tunneling, and partial tunneling. The distinction among the three depends on the support of the incident wave packet’s energy distribution in relation to the shape of the barrier. Non-tunneling happens when the energy distribution of the quantum particle lies above the maximum of the potential barrier. Otherwise, full-tunneling process occurs when the energy distribution of the particle is below the minimum of the potential barrier. For this process, the obtained traversal time is interpreted as the tunneling time. Finally, the partial-tunneling process occurs when the energy distribution lies between the minimum and maximum of the potential barrier. This signifies that the quantum particle tunneled only through some portions of the potential barrier. We argue that the duration for a partial-tunneling process should not be interpreted as the tunneling time but instead as a partial traversal time to differentiate it from the full-tunneling process. We then show that a full-tunneling process is always instantaneous, while a partial-tunneling process takes a non-zero amount of time. We are then led to the hypothesis that experimentally measured non-zero and vanishing tunneling times correspond to partial- and full-tunneling processes, respectively.

The weak equivalence principle (WEP) in the quantum regime has been the subject of many studies with a broad range of approaches to the problem. Here, we tackle the problem anew through the time of arrival (TOA) operator approach. This is done by constructing the TOA operator for a nonrelativistic and structureless particle that is projected upward in a uniform gravitational field with an intended arrival point below the classical turning point. The TOA operator is constructed under the constraint that the inertial and gravitational masses are equivalent and that Galilean invariance is preserved. These constraints are implemented by Weyl quantization of the corresponding classical TOA function for the projectile. The expectation value of the TOA operator is explicitly shown to be equal to the classical time of arrival plus mass-dependent quantum correction terms, implying incompatibility of the WEP with quantum mechanics. The full extent of the violation of the WEP is shown through the mass dependence of TOA distribution for the projectile.