ABSTRACT
Two-dimensional electronic spectroscopy (2DES) can be implemented with different geometries, e.g., BOXCARS, collinear, and pump-probe geometries. The pump-probe geometry has the advantage of overlapping only two beams and reducing phase cycling steps. However, its applications are typically limited to observing the dynamics with single-quantum coherence and population, leaving the challenge to measure the dynamics of the double-quantum (2Q) coherence, which reflects the many-body interactions. We demonstrate an experimental technique in 2DES under pump-probe geometry with a designed pulse sequence and the signal processing method to extract 2Q coherence. In the designed pulse sequence, with the probe pulse arriving earlier than the pump pulses, our measured signal includes the 2Q signal as well as the zero-quantum signal. With phase cycling and data processing using causality enforcement, we extract the 2Q signal. The proposal is demonstrated with rubidium atoms. We observe the collective resonances of two-body dipole-dipole interactions in both the D1 and D2 lines.
ABSTRACT
Developing from transient absorption (TA) spectroscopy, two-dimensional (2D) spectroscopy with pump-probe geometry has emerged as a versatile approach for alleviating the difficulty in implementing 2D spectroscopy with other geometries. However, the presence of cross-phase modulation (XPM) in TA spectroscopy introduces significant spectral distortions, particularly when the pump and probe pulses overlap. We demonstrate that this phenomenon is extended to the 2D spectroscopy with pump-probe geometry and the XPM is induced by the interference of the two pump pulses. We present the oscillatory behavior of XPM in the 2D spectrum and its displacement with respect to the waiting time delay through both experimental measurements and numerical simulations. Additionally, we explore the influence of probe pulse chirp on XPM and discover that by compressing the chirp, the impact of XPM on the desired signal can be reduced.
ABSTRACT
Enantiodetection of chiral molecules is important to chemical reaction control and biological function designs. Traditional optical methods of enantiodetection rely on the weak magnetic-dipole or electric-quadrupole interactions, and in turn suffer from the weak signal and low sensitivity. We propose a new optical enantiodetection method to determine the enantiomeric excess via two-dimensional (2D) spectroscopy of the chiral mixture driven by three electromagnetic fields. The quantities of left- and right-handed chiral molecules are reflected by the intensities of different peaks on the 2D spectrum, separated by the chirality-dependent frequency shifts resulting from the relative strong electric-dipole interactions between the chiral molecules and the driving fields. Thus, the enantiomeric excess can be determined via the intensity ratio of the peaks for the two enantiomers.
