Theory of enantiomeric control in dimethylallene using achiral light

Abstract

Extensive control over enantiomer populations using achiral light is computationally demonstrated for J, MJ-selected 1,3 dimethylallene. In particular, by altering the detuning of one of three lasers incident on an J, MJ-polarized racemic mixture, one can alter the enantiomeric excess from ≈93% of the L enantiomer to ≈93% of the D enantiomer.

Adaptive Femtosecond Quantum Control

“…This opens the door to a number of qualitatively new experimental schemes, which exploit the full vectorial temporal response of quantum systems. It allows to address stereochemical aspects in quantum control such as chiral selectivity, where polarization-shaped laser pulses are a crucial ingredient [31][32][33][34][35][36]. The optical control of lattice vibrations [156] and the generation and characterization of attosecond light pulses [130,131] are further examples of numerous new perspectives.…”

“…Moreover, as both µ(t) and E(t) are vectorial quantities, it is apparent that the polarization of the electric field can significantly influence the outcome of a given process. In recent years it has been shown by Brumer, Shapiro and coworkers [31,32], by Bychkov et al [33] and by Fujimura, Manz and coworkers [34][35][36] that the manipulation of the polarization state of the control field is a crucial ingredient for achieving selectivity in chiral systems. Chapters 3.4.2 and 5 deal with the questions how such time-dependent polarization profiles can be generated in the near-IR, and how they can be transferred to the visible/UV spectral range.…”

“…The application of time-dependent polarization states that can thus be generated has been suggested, for example, for the generation [130,131] and characterization [132] of attosecond light pulses, for the optical control of lattice vibrations [133] and the selective production of enantiomers [31][32][33][34][35][36]. The adaptive shaping of complex polarization profiles within a learning loop has been demonstrated by our group in an optical demonstration experiment [134], and Oron et al have used spectral modulation of phase and polarization direction in coherent anti-Stokes Raman spectroscopy (CARS) [135].…”

Geometrical Optimization Approach to Isomerization: Models and Limitations

“…Here the polarization plays an important role [34][35][36][37][38], but the linear components of the polarized field can work separately if there operates a mechanism for breaking the parity of the system [39][40][41][42][43] or in the simpler scenario where the molecule is aligned with the electric field [32,33]. Even recent approaches with strong fields, based on the role of Stark effects [47][48][49][50] or the use of counterdiabatic pulses to accelerate adiabatic passage [51] were proposed and tested.…”

“…-18]. Numerical results using N-level Hamiltonians under long pulses and wave-packet calculations in reduced (1 or 2)-dimensional models for short pulse dynamics have also shown great promise in the possibility of driving isomerization reactions [19][20][21][22][23][24][25][26][27][28][29][30][31] and even distinguishing optical isomers or purifying a racemate mixture [32][33][34][35][36][37][38][39][40][41][42][43][44]. The most general models of population transfer were applied.…”