Quantum field theory of optical birefringence phenomena I. Linear and nonlinear optical rotation

Atkins, Peter; Barron, Laurence D.

doi:10.1098/rspa.1968.0088

Cited by 60 publications

(6 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Chiroptical effects at thirdorder have first been discussed by Akhmanov 75 and Barron 76 in the early years of nonlinear optics, and aspects of the theory have since been developed further. 77,78 Optical activity arises in the nonlinear response if one goes beyond the electric dipole approximation in eq.…”

Section: Third-order Nonlinear Chiroptical Effects In a Liquidmentioning

confidence: 99%

Nonlinear optical spectroscopy of chiral molecules

2005

View full text Add to dashboard Cite

We review nonlinear optical processes that are specific to chiral molecules in solution and on surfaces. In contrast to conventional natural optical activity phenomena, which depend linearly on the electric field strength of the optical field, we discuss how optical processes that are nonlinear (quadratic, cubic, and quartic) functions of the electromagnetic field strength may probe optically active centers and chiral vibrations. We show that nonlinear techniques open entirely new ways of exploring chirality in chemical and biological systems: The cubic processes give rise to nonlinear circular dichroism and nonlinear optical rotation and make it possible to observe dynamic chiral processes at ultrafast time scales. The quadratic second-harmonic and sum-frequency-generation phenomena and the quartic processes may arise entirely in the electric-dipole approximation and do not require the use of circularly polarized light to detect chirality. They provide surface selectivity and their observables can be relatively much larger than in linear optical activity. These processes also give rise to the generation of light at a new color, and in liquids this frequency conversion only occurs if the solution is optically active. We survey recent chiral nonlinear optical experiments and give examples of their application to problems of biophysical interest.

show abstract

Section: Third-order Nonlinear Chiroptical Effects In a Liquidmentioning

confidence: 99%

Nonlinear optical spectroscopy of chiral molecules

2005

View full text Add to dashboard Cite

show abstract

“…The following account begins, in section 2, by emphasizing the difference between the calculation of an optical force-employed when the initial and final states of the system (including the radiation states) are identical-and calculating a rate expression to describe an optical process in which the initial and final states differ. In connection with the present work, it is crucial to understand that chirality effects in optical trapping have a fundamental relationship to optical rotation [41,42] (i.e. a rotation of optical polarization).…”

Section: Introductionmentioning

confidence: 99%

Chiral discrimination in optical trapping and manipulation

Bradshaw¹,

Andrews²

2014

New J. Phys.

View full text Add to dashboard Cite

When circularly polarized light interacts with chiral molecules or nanoscale particles powerful symmetry principles determine the possibility of achieving chiral discrimination, and the detailed form of electrodynamic mechanisms dictate the types of interaction that can be involved. The optical trapping of molecules and nanoscale particles can be described in terms of a forward-Rayleigh scattering mechanism, with trapping forces being dependent on the positioning within the commonly non-uniform intensity beam profile. In such a scheme, nanoparticles are commonly attracted to local potential energy minima, ordinarily towards the centre of the beam. For achiral particles the pertinent material response property usually entails an electronic polarizability involving transition electric dipole moments. However, in the case of chiral molecules, additional effects arise through the engagement of magnetic counterpart transition dipoles. It emerges that, when circularly polarized light is used for the trapping, a discriminatory response can be identified between left-and righthanded polarizations. Developing a quantum framework to accurately describe this phenomenon, with a tensor formulation to correctly represent the relevant molecular properties, the theory leads to exact analytical expressions for the associated energy landscape contributions. Specific results are identified for liquids and solutions, both for isotropic media and also where partial alignment arises due to a static electric field. The paper concludes with a pragmatic analysis of the scope for achieving enantiomer separation by such methods.

show abstract

“…Molecules with this property exhibit a variety of optical effects. These include routine spectroscopic techniques such as optical rotation, , circular dichroism, circular differential Rayleigh and Raman scattering, , circularly polarized luminescence, and their less common higher-order counterparts as well as several other nonlinear chiroptical processes such as sum/difference frequency generation spectroscopy and harmonic generation. − Differentiating between enantiomers rests fundamentally on the Curie dissymmetry principle, which necessitates the presence of a second reference object or system that is also handed. Often circularly polarized light plays the role of discriminator in spectroscopic processes.…”

Section: Introductionmentioning

confidence: 99%

Discriminatory Resonance Energy Transfer Mediated by a Third Molecule

Salam

2021

J. Phys. Chem. A

View full text Add to dashboard Cite

Relay of resonant excitation energy between two chiral molecules by an inert third particle is studied using molecular quantum electrodynamics theory. A single virtual photon propagates between each interacting pair. Fourth-order diagrammatic time-dependent perturbation theory is employed to compute the matrix element. Rate terms dependent upon the chirality of the donor and acceptor species are extracted using the Fermi golden rule. Interestingly, the mediated rate is discriminatory. For freely tumbling particles it exhibits an inverse-square dependence on each interparticle separation distance, indicating a purely radiative exchange mechanism. Furthermore, the isotropic rate is found to be a maximum for a collinear geometry and vanishes when the angle between the donor, mediator, and acceptor is 90°. The indirect rate is compared with direct transfer between two chiral molecules. Insight is gained into discriminatory migration of energy in a dielectric medium.

show abstract

Quantum field theory of optical birefringence phenomena I. Linear and nonlinear optical rotation

Cited by 60 publications

References 5 publications

Nonlinear optical spectroscopy of chiral molecules

Nonlinear optical spectroscopy of chiral molecules

Chiral discrimination in optical trapping and manipulation

Discriminatory Resonance Energy Transfer Mediated by a Third Molecule

Contact Info

Product

Resources

About