Probing chirality fluctuations in molecules by nonlinear optical spectroscopy.

@article{Mann2014ProbingCF,
  title={Probing chirality fluctuations in molecules by nonlinear optical spectroscopy.},
  author={Niklas Mann and Peter Nalbach and Shaul Mukamel and Michael Thorwart},
  journal={The Journal of chemical physics},
  year={2014},
  volume={141 23},
  pages={
          234305
        }
}
Symmetry breaking caused by geometric fluctuations can enable processes that are otherwise forbidden. An example is a perylene bisimide dyad whose dipole moments are perpendicular to each other. Förster-type energy transfer is thus forbidden at the equilibrium geometry since the dipolar coupling vanishes. Yet, fluctuations of the geometric arrangement have been shown to induce finite energy transfer that depends on the dipole variance, rather than the mean. We demonstrate an analogous effect… 
4 Citations

Isolating the chiral contribution in optical two-dimensional chiral spectroscopy using linearly polarized light.

It is found that in both cases an achiral signal from an isotropic system can be completely eliminated by small manipulations of the relative angles between the linear polarizations of the four input laser pulses.

Vibronic Intramolecular Resonant Energy Transfer along More than 5 nm: Synthesis of Dyads for a Re-Examination of the Distance Function of FRET.

Dyads of chromophores with orthogonal transition moments and sequences of aliphatic cage-structures as spacers were prepared where resonance energy transfer (FRET) proceeded in contrast to Förster's

References

SHOWING 1-10 OF 22 REFERENCES

Novel coherent two-dimensional optical spectroscopy probes of chirality exchange and fluctuations in molecules.

We demonstrate how stochastic transitions between molecular configurations with opposite senses of chirality may be probed by 2D optical signals with specific pulse polarization configurations. The

Förster resonant energy transfer in orthogonally arranged chromophores.

The dyads presented here are a first example that shows with extreme clarity the decisive role vibrational motion plays in energy transfer processes.

Noise-induced Förster resonant energy transfer between orthogonal dipoles in photoexcited molecules.

We show that Förster resonance energy transfer (FRET) in an orthogonally arranged donor-acceptor pair can be induced by environmental noise, although direct transfer is prohibited. Environmental

High-resolution spectroscopic studies and theory of parity violation in chiral molecules.

The high-resolution spectroscopic approach toward the study of intramolecular dynamics, emphasizing molecular parity violation, is reviewed, and the promises of detecting and accurately measuring parity-violating energy differences Delta(pv) E on the order of 10(11) J mol(1) in enantiomers of chiral molecules are discussed.

Generalization of the Forster resonance energy transfer theory for quantum mechanical modulation of the donor-acceptor coupling.

The Forster resonance energy transfer theory is generalized for inelastic situations with quantum mechanical modulation of the donor-acceptor coupling and has new elastic and inELastic terms, depending sensitively on the value of the minimum energy torsional angle.

Two-dimensional nonlinear optical activity spectroscopy of coupled multi-chromophore system.

It is theoretically shown that novel 2D optical activity measurement techniques based on three- and four-wave-mixing schemes are of use to obtain the 2D spectrum of a chiral molecule.

Optical signatures of molecular dissymmetry: combining theory with experiments to address stereochemical puzzles.

This Account explores how modern theory, synthesis, and spectroscopy can be used in concert to elucidate the symmetry and dissymmetry of molecules and their assemblies and defines atomic and group contributions to optical rotation (OR).

Limits on fluorescence detected circular dichroism of single helicene molecules.

The dissymmetry factors of single chiral fluorophores are found not to differ significantly from the bulk value of |g| < 10(-4) at 457 nm, and compensation should be made to avoid artifacts brought by linear dichroism in single immobilized molecules.

Beyond Förster resonance energy transfer in biological and nanoscale systems.

Various ways that electronic energy transfer is promoted by mechanisms beyond those explicitly considered in Forster RET theory are considered.

Rotating wave approximation: systematic expansion and application to coupled spin pairs

Abstract:We propose a new treatment of the dynamics of a periodically time-dependent Liouvillian by mapping it onto a time-independent problem and give a systematic expansion for its effective