Chiral Distinction by Ultrashort Laser Pulses: Electron Wavepacket Dynamics Incorporating Magnetic Interactions

The qualitative and quantitative distinction of enantiomers is one of the key issues in chemical analysis. In the last years, circular dichroism (CD) has been combined with laser ionization mass spectrometry (LIMS), applying resonance enhanced multiphoton ionization (REMPI) with ultrashort laser pulses. We present theoretical investigations on the CD in the populations of the first electronic excited state of the REMPI process, caused by the interaction of 3-methylcyclopentanone with either left or right circular polarized fs-laser pulses. For this we performed multistate laser driven many electron dynamics based on ab initio electronic structure calculations, namely, TD-CIS(D)/6-311++(2d,2p). For a theoretical description of these experiments, a complete description of the field-dipole correlation is mandatory, including both electric field electric dipole and magnetic field magnetic dipole interactions. The effect of various pulse parameters on the CD are analyzed and compared with experimental results to gain further understanding of the key elements for an optimal distinction of enantiomers.