Optical activity and time reversal

The rôle of time reversal symmetry in natural and magnetic optical activity is discussed. Natural optical rotation is shown to be generated by an anti-hermitian odd parity time-even operator and magnetic optical rotation by an anti-hermitian even parity time-odd operator. This shows that lack of time reversal invariance is not the source of natural optical rotation and that free atoms can show natural optical rotation without violating reversality, which leads to a fundamental distinction between the conditions necessary for natural optical rotation and a permanent space-fixed electric dipole moment. General transition optical activity and polarizability tensors between components of degenerate states are discussed with reference to possible new Raman experiments and new contributions to discriminating intermolecular forces between chiral molecules. Time reversal symmetry also leads to a new criterion for chiral objects and to the concept that natural optical activity provides an example of spontaneous symmetry breaking with respect to CP.     

Paraelectricity in magnetized massless QED

We show that the chiral-symmetry-broken phase of massless QED in the presence of a magnetic field exhibits strong paraelectricity. A large anisotropic electric susceptibility develops in the infrared region, where most of the fermions are confined to their lowest Landau level, and dynamical mass and anomalous magnetic moment are generated via the magnetic catalysis mechanism. The nonperturbative nature of this effect is reflected in the dependence of the electric susceptibility on the fine-structure constant. The strong paraelectricity is linked to the electric dipole moments of the particle-antiparticle pairs that form the chiral condensate. The significant electric susceptibility can be used as a probe to detect the realization of the magnetic catalysis of chiral symmetry breaking in physical systems.     

Hydrogen bonding in homochiral dimers of hydroxyesters studied by Raman optical activity spectroscopy

Spectroscopic analysis of homochiral dimerization is important for the understanding of the homochirality of life and enantioselective catalysis. In this paper, (S)‐methyl lactate and related molecules were studied to provide detailed structural information on hydrogen bonding in homochiral dimers of chiral α‐hydroxyesters through the experimental and theoretical study of Raman optical activity. Different homochiral dimers can be distinguished by comparing their simulated Raman optical activity spectra with the experimental results. Hydrogen bonding motions are decoded with the aid of vibrational motion analysis, which are apparently involved in vibrational motions below 800 cm^–1. A common feature related to the chain‐bending mode also indicates the absolute configuration of methyl lactate and related molecules. The differing behavior of electric dipole–electric quadrupole invariants (β(A)²) compared with the electric dipole–magnetic dipole invariant (β(G′)²), suggests that the intermolecular hydrogen bonding motion behaves differently from the intramolecular one in the asymmetric molecular electric and magnetic fields. These results may help understand hydrogen‐bonded self‐recognition and other dynamical features in chiral recognition. Copyright © 2011 John Wiley & Sons, Ltd.     

Orbital-angular-momentum based origin of Rashba-type surface band splitting

We propose that the existence of local orbital angular momentum (OAM) on the surfaces of high-Z materials plays a crucial role in the formation of Rashba-type surface band splitting. Local OAM state in a Bloch wave function produces an asymmetric charge distribution (electric dipole). The surface-normal electric field then aligns the electric dipole and results in chiral OAM states and the relevant Rashba-type splitting. Therefore, the band splitting originates from electric dipole interaction, not from the relativistic Zeeman splitting as proposed in the original Rashba picture. The characteristic spin chiral structure of Rashba states is formed through the spin-orbit coupling and thus is a secondary effect to the chiral OAM. Results from first-principles calculations on a single Bi layer under an external electric field verify the key predictions of the new model.     

On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide,methyl hydroperoxide and dimethyl peroxide

The chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculated as mixed linear response functions of the electric and magnetic dipole moment operators. Applying a canonical transformation of the Hamiltonian, which reformulates the magnetic dipole moment operator in terms of the operator for the torque acting on the electrons, the ORP of a molecule can be partitioned into atomic and group contributions. In the present work, we investigate the transferability of such individual contributions in a series of small, chiral molecules: hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide. The isotropic atomic or group contributions have been evaluated for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules.     

Dependence of ligand fields in paramagnetic crystals on thermal changes in their structures

Paramagnetic behaviours of the salts of the iron group depend upon the asymmetric ligand fields acting upon the central paramagnetic ion, as also upon the structure and packing of the crystal lattice. A general picture of the energy levels of the paramagnetic ions is, available from the ligand field theory, based upon the coordinated data on X-ray structure, magnetic susceptibility and anisotropy, e.p.r and optical absorption spectra. When all these facts have been taken into account it is observed that there is an almost universal discrepancy between the observed thermal magnetic behaviours, particularly the anisotropy and those theoretically predicted on the assumption that the ligand fields are independent of temperature. The discrepancy cannot usually be covered by the change in the fields due to normal thermal expansion of the lattice. It is pointed out that these may be occasionally due to electric dipole ordering in the crystals at certain temperatures but more generally due to continuous types of transition in the crystal lattice with temperature, which change the lattice packing in an anomalous manner and thus cause a thermal variation in the asymmetric ligand fields.     

Polarization-independent magnetic control of the light phase in a chiral optical fiber

The proposition is made to fine-tune the phase of an unpolarized guided mode in a chiral optical waveguide, or fiber, by a static magnetic field applied in the direction of the light propagation. The core of the fiber should consist of randomly oriented chiral molecules, and the magnetic field-induced change of the refractive index would be due to the magnetochiral effect [1]. Although the magnetochiral birefringence is very small for magnetic field strengths obtainable under routine laboratory conditions, the induced phase shift for a given magnetic field should be maximized by increasing the pathlength of light inside the field. This would be technically achievable by winding the optical fiber axially many times around the electric solenoid that generates the magnetic field, in such a way that the path of the light inside the fiber follows closely and over a distance as long as possible the magnetic induction lines.     

Strong near-field couplings of anapole modes and formation of higher-order electromagnetic modes in stacked all-dielectric nanodisks

We theoretically study the near-field couplings of two stacked all-dielectric nanodisks, where each disk has an electric anapole mode consisting of an electric dipole mode and an electric toroidal dipole (ETD) mode. Strong bonding and anti-bonding hybridizations of the ETD modes of the two disks occur. The bonding hybridized ETD can interfere with the dimer's electric dipole mode and induce a new electric anapole mode. The anti-bonding hybridization of the ETD modes can induce a magnetic toroidal dipole (MTD) response in the disk dimer. The MTD and magnetic dipole resonances of the dimer form a magnetic anapole mode. Thus, two dips associated with the hybridized modes appear on the scattering spectrum of the dimer. Furthermore, the MTD mode is also accompanied by an electric toroidal quadrupole mode. The hybridizations of the ETD and the induced higher-order modes can be adjusted by varying the geometries of the disks. The strong anapole mode couplings and the corresponding rich higher-order mode responses in simple all-dielectric nanostructures can provide new opportunities for nanoscale optical manipulations.     

Optical second harmonic generation induced by picosecond terahertz pulses in centrosymmetric antiferromagnet NiO

Optical second harmonic generation at the photon energy of 2?ω = 2eV in the model centrosymmetric antiferromagnet NiO irradiated with picosecond terahertz pulses (0.4–2.5 THz) at room temperature is detected. The analysis of experimental results shows that induced optical second harmonic generation at the moment of the impact of a terahertz pulse arises through the electric dipole mechanism of the interaction of the electric field of a pump pulse with the electron subsystem of NiO. Temporal changes in optical second harmonic generation during 7 ps after the action of the pulse are also of an electric dipole origin and are determined by the effects of propagation of the terahertz pulse in a NiO platelet. Coherent oscillations of spins at the antiferromagnetic resonance frequency induced by the magnetic component of the terahertz pulse induce a relatively weak modulation of magnetic dipole optical second harmonic generation.     

Ab initio treatment of optical second harmonic generation in NiO

In this Letter we develop a new systematic approach to study optical second harmonic generation in NiO, on both the (001) surface and the bulk. NiO is modeled as a doubly embedded cluster on which two highly correlated quantum chemistry methods are applied in order to obtain the wave functions of all the intragap d states and the low lying charge transfer states. The optical gap is calculated and the electric dipole, magnetic dipole, and electric quadrupole contributions to the second order susceptibility tensor are computed for the first time from first principles. Going beyond the electric dipole approximation gives new insight into the experimentally observed spectrum. A method is proposed for monitoring the spin dynamics of the NiO(001) surface.     

Comparison of the third-order dispersion terms of interaction between chiral molecules

Using a quantum electrodynamic approach, the coupling between chiral molecules derived from the exchange of three virtual photons of the electric dipole type is investigated. The resulting interaction potential, which involves the first nonlinear polarizability of the molecules, is compared with a previously derived interaction potential involving the optical activity of the molecules; the latter is accounted for by the exchange of two virtual photons, one being electric dipolar and the other being electric quadrupolar or magnetic dipolar. The symmetry properties of the new term is considered and its quasi-static limit is derived. It appears that the two interaction terms, which both are third-order dispersion processes, might have the same order of magnitude; thus none can a priori be neglected and both might equally contribute to the possibility of a helical ordering.     

Magnetic and Mössbauer Studies of Fe<Subscript>76</Subscript>Mo<Subscript>8</Subscript>Cu<Subscript>1</Subscript>B<Subscript>15</Subscript> Amorphous Alloy

“Zero field”-Mössbauer and magnetization measurements have been performed on an amorphous Fe₇₆Mo₈Cu₁B₁₅ alloy in the temperature range of (10-340) K. The room-temperature Mössbauer spectrum exhibits magnetic dipole and electric quadrupole interactions. At approximately 306 K, the magnetic interactions vanish and the alloy shows fully paramagnetic behavior. On the other hand, the relative representation of paramagnetic component becomes weak with decreasing temperature and below 220 K the magnetic dipole interactions prevail. Below this temperature an anomaly in the low-temperature dependencies of ac susceptibility and of magnetization, measured during cooling the specimen from 340 K down to 20 K is observed. The anomaly on the magnetization curve vanishes in the field of 200 Oe.     

Photoexcitation in two-dimensional topological insulators

One of the most fascinating challenges in Physics is the realization of an electron-based counterpart of quantum optics, which requires the capability to generate and control single electron wave packets. The edge states of quantum spin Hall (QSH) systems, i.e., two-dimensional (2D) topological insulators realized in HgTe/CdTe and InAs/GaSb quantum wells, may turn the tide in the field, as they do not require the magnetic field that limits the implementations based on quantum Hall effect. However, the band structure of these topological states, described by a massless Dirac fermion Hamiltonian, prevents electron photoexcitation via the customary vertical electric dipole transitions of conventional optoelectronics. So far, proposals to overcome this problem are based on magnetic dipole transitions induced via Zeeman coupling by circularly polarised radiation, and are limited by the g-factor. Alternatively, optical transitions can be induced from the edge states to the bulk states, which are not topologically protected though.Here we show that an electric pulse, localized in space and/or time and applied at a QSH edge, can photoexcite electron wavepackets by intra-branch electrical transitions, without invoking the bulk states or the Zeeman coupling. Such wavepackets are spin-polarised and propagate in opposite directions, with a density profile that is independent of the initial equilibrium temperature and that does not exhibit dispersion, as a result of the linearity of the spectrum and of the chiral anomaly characterising massless Dirac electrons. We also investigate the photoexcited energy distribution and show how, under appropriate circumstances, minimal excitations (Levitons) are generated. Furthermore, we show that the presence of a Rashba spin–orbit coupling can be exploited to tailor the shape of photoexcited wavepackets. Possible experimental realizations are also discussed.     

Oscillator strengths of optical transitions of a cylindrical shell: Crossed static electric and magnetic fields

The single-electron eigenstates of a cylindrical shell are determined as functions of the applied crossed electric and magnetic fields in the effective-mass approximation. The system considered consists of donor charges taken to be uniformly distributed within an inner core of infinitely long length. The core is concentrically enveloped by a semiconducting material of finite thickness; which is essentially the host material. This configuration of the donor charges sets up a spatially varying electric field nonetheless with only the radial component. In addition, a uniform magnetic field is applied parallel to the axis of symmetry of the inner core. As is well known, the axial applied magnetic field lifts the double degeneracies of the electron’s subbands characterized by the same azimuthal quantum numbers which differ only in sign. The main effect of increasing the external electric field is to elevate the various energy subbands, more or less to the same extent, to higher values. Further, evaluations of the oscillator strengths of optical transitions of the cylindrical shell are carried out within the dipole approximation. The radiation field is taken to be that of circularly polarized light incident along the axis of the core. The oscillator strengths of optical transitions are found to increase with an increase of the applied magnetic field, particularly in the regime of small magnetic fields. In contrast, the oscillator strengths of these optical interactions become suppressed as the donor charge density is increased.     

Combined Magneto-Electric Spin Resonance of Impurity Ho Ions in Synthetic Forsterite

Continuous-wave electron paramagnetic resonance spectra of impurity holmium ions in synthetic forsterite have been studied on an ELEXSYS E580 spectrometer equipped with a cylindrical dielectric resonator ER4118MD5-W1 of the Flexline series. Resonance lines of the anomalous shape demonstrating the absorption contour instead of its derivative were observed at the conventional operation mode with the magnetic field modulation. The conditions of the appearance of anomalous signals and their characteristics have been studied. The anomalous lines shape effect was explained by the simultaneous excitation of magnetic dipole and electric quadrupole transitions between electron–nuclear spin sublevels of the holmium ions.     

Depending on the electric and magnetic field of the linear optical absorption and rectification coefficient in triple quantum well

In this study, the alteration of the potential profile, the energy levels, the dipole matrix element and the resonant peaks of the linear optical absorption (OA) and optical rectification (OR) coefficients in GaAs/GaAlAs triple quantum well (TQW) are calculated as dependent on the applied electric field and the magnetic field. The results show that the shape of confined potential profile, the energy levels and the dipole moment matrix elements are changed as dependent on the external fields. Also, the resonant peaks of the OA and OR coefficients depend on the applied external field effects. Therefore, I hope that these results will provide important improvement in semiconductor device applications, for suitable choice of electric and magnetic field values. It may particularly be useful in technological applications that the structure of TQW changes with the strength and direction of the external electric field.     

Nondipole optical scattering from liquids and nanoparticles

Nondipolar contribution to optical scattering in liquids and nanoparticle suspensions has been discerned for the first time from the dominant electric dipole scattering by assigning the observed polarization and azimuthal angular distribution of scattered polarized light to pure magnetic dipole and/or electric quadrupole radiation and ruling out other (the impurity of laser polarization, multiple scattering, optical activity, and optical anisotropy) explanations. The observed scattering has potential use in the optical study of nanoparticles.     

The separation of magnetic dipole and electric quadrupole contributions to Raman optical activity via the Raman-induced Kerr effect

A procedure is presented for the complete separation of magnetic dipole and electric quadrupole contributions to Raman optical activity using the Raman-induced Kerr effect. The method involves carrying out a series of co/counter-propagating and frequency interchange experiments. Feasibility is discussed as well as application to some recent experimental observations in α-quartz.     

Spin physics in solid helium: Experimental results and applications

We have observed optical pumping signals from Cs atoms trapped in solid⁴He. While the longitudinal electronic spin relaxation timeT ₁ is found to be in the range of 1–2 s, the transverse relaxation timeT ₂, as inferred from magnetic resonance linewidths has a lower bound of 150 s, and is determined by magnetic field inhomogeneities. We present a quantitative discussion of how paramagnetic species trapped in solid He might be used in a highly sensitive search for permanent atomic electric dipole moments.     

Efficiency of the structure analysis of complex molecules in the gas phase by their optical rotation

It was shown in the dipole approximation of optical rotation that in the general case only in orientationally anisotropic vapors is the rotational force dependent on the intramolecular orientation of both the electric and magnetic dipole moments. Expressions relating the optical rotational force to the intramolecular orientation of these moments, the orientational distribution in an anisotropic ensemble, and the configuration of a measurement have been obtained. Calculated dependences of the rotational force on the intramolecular orientation of the magnetic moment at a fixed electric moment and “rotational force excitation spectra” obtained for different types of rigid asymmetric top molecules and rotational contours are presented. It is proposed to measure the intramolecular orientation of the electric and magnetic dipole moments with the use of the rotational force normalized to that detected in the case of observation at a “magic” angle to the direction of the exciting light electric vector. Institute of Molecular and Atomic Physics of the Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 843–849, November–December, 1998.