Anisotropic Dissymmetry Factor,<i>g</i>: Theoretical Investigation on Single Molecule Chiroptical Spectroscopy

Wakabayashi, Masamitsu; Yokojima, Satoshi; Fukaminato, Tuyoshi; Shiino, Ken Ichi; Irie, Masahiro; Nakamura, Shinichiro

doi:10.1021/jp409559t

Cited by 63 publications

(68 citation statements)

References 106 publications

(134 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The strengths of chiroptical responses were compared across different experiments using the Kuhn dissymmetry factor, 80 , 81 g abs : where A L (or A R ) is the absorbance of left- (or right-) handed circularly polarized light at λ max in the CD spectra. The term ( A L + A R )/2 corresponds to the unpolarized UV–vis absorption, rendering g abs independent of the sample concentration used in the measurement.…”

Section: Results and Discussionmentioning

confidence: 99%

Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

et al. 2018

View full text Add to dashboard Cite

Self-assembled helical polymers hold great promise as new functional materials, where helical handedness controls useful properties such as circularly polarized light emission or electron spin. The technique of subcomponent self-assembly can generate helical polymers from readily prepared monomers. Here we present three distinct strategies for chiral induction in double-helical metallopolymers prepared via subcomponent self-assembly: (1) employing an enantiopure monomer, (2) polymerization in a chiral solvent, (3) using an enantiopure initiating group. Kinetic and thermodynamic models were developed to describe the polymer growth mechanisms and quantify the strength of chiral induction, respectively. We found the degree of chiral induction to vary as a function of polymer length. Ordered, rod-like aggregates more than 70 nm long were also observed in the solid state. Our findings provide a basis to choose the most suitable method of chiral induction based on length, regiochemical, and stereochemical requirements, allowing stereochemical control to be established in easily accessible ways.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

et al. 2018

View full text Add to dashboard Cite

show abstract

“…For quantum systems such as small molecules and semiconductor nanocrystals, whose dimensions are much smaller than the optical wavelength, the rotatory strength is given by Rosenfeld’s formula 25 where | i 〉 and | f 〉 are the initial and final states of the transition, and d and m are the electric and magnetic dipole moments. The strength of enantioselectivity in the interaction of a quantum system with circularly polarized light is characterized by the dissymmetry factor , which is the ratio of the rotatory strength to the full dipole absorption rate 26 , …”

Section: Resultsmentioning

confidence: 99%

Mixing of quantum states: A new route to creating optical activity

Baimuratov

Tepliakov

Gun’ko

et al. 2016

Sci Rep

View full text Add to dashboard Cite

The ability to induce optical activity in nanoparticles and dynamically control its strength is of great practical importance due to potential applications in various areas, including biochemistry, toxicology, and pharmaceutical science. Here we propose a new method of creating optical activity in originally achiral quantum nanostructures based on the mixing of their energy states of different parities. The mixing can be achieved by selective excitation of specific states or via perturbing all the states in a controllable fashion. We analyze the general features of the so produced optical activity and elucidate the conditions required to realize the total dissymmetry of optical response. The proposed approach is applicable to a broad variety of real systems that can be used to advance chiroptical devices and methods.

show abstract

“…This feature is illustrated in Table 1. The large absorption upon the electric dipole transition is seen to result in g-factors in the range from 10 −4 to 10 −3 , which is typical for small chiral molecules [29]. As the magnetic dipole absorption is about 10 4 weaker than the electric dipole one, the g-factors of the magnetic dipole transitions can be of the order of unity, indicating a strong chiroptical response.…”

Section: Nanorodmentioning

confidence: 82%

Engineering Optical Activity of Semiconductor Nanocrystals via Ion Doping

et al. 2016

View full text Add to dashboard Cite

Controlling the strength of enantioselective interaction of chiral inorganic nanoparticles with circularly polarized light is an intrinsically interesting subject of contemporary nanophotonics. This interaction is relatively weak, because the chirality scale of nanoparticles is much smaller than the optical wavelength. Here we theoretically demonstrate that ion doping provides a powerful tool of engineering and enhances optical activity of semiconductor nanocrystals. We show that by carefully positioning ionic impurities inside the nanocrystals, one can maximize the rotatory strengths of intraband optical transitions, and make them 100 times larger than the typical rotatory strengths of small chiral molecules.

show abstract

Anisotropic Dissymmetry Factor,g: Theoretical Investigation on Single Molecule Chiroptical Spectroscopy

Cited by 63 publications

References 106 publications

Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers

Mixing of quantum states: A new route to creating optical activity

Engineering Optical Activity of Semiconductor Nanocrystals via Ion Doping

Contact Info

Product

Resources

About