Fifth-Order Raman Spectroscopy of Liquid Benzene:  Experiment and Theory

Abstract

The heterodyned fifth-order Raman response of liquid benzene has been measured and characterized by exploiting the passive-phase stabilization of diffractive optics. This result builds on our previous work with liquid carbon disulfide and extends the spectroscopy to a new liquid for the first time. The all-parallel and Dutch Cross polarization tensor elements are presented for both the experimental results and a finite-field molecular dynamics simulation. The overall response characteristics are similar to those of liquid carbon disulfide: a complete lack of signal along the pump delay, an elongated signal along the probe delay, and a short-lived signal along the time diagonal. Of particular interest is the change in phase between the nuclear and electronic response along the probe delay and diagonal which is not seen in CS2. Good agreement is achieved between the experiment and the finite-field molecular dynamics simulation. The measurement of the low-frequency Raman two-time delay correlation function indicates the intermolecular modes of liquid benzene to be primarily homogeneously broadened and that the liquid loses its nuclear rephasing ability within 300 fs. This rapid loss of nuclear correlations indicates a lack of modal character in the low-frequency motions of liquid benzene. This result is a validation of the general nature of the technique and represents an important step forward with respect to the use of nonlinear spectroscopy to directly access information on the anharmonic motions of liquids.

Rattling the cage: Micro- to mesoscopic structure in liquids as simple as argon and as complicated as water

“…[53] Other techniques have been developed that measure higher order correlation functions depending on three or even four time intervals, such as, (infrared) photon echoes and 2D-IR, [54][55][56][57] fifth-order spectroscopy, [58][59][60][61] and Raman photon echoes. [62][63][64] Although such higher order techniques can in principle extract more information, generally the depth of analysis is limited by poorer signal-to-noise ratios.…”

Purely absorptive three-dimensional infrared spectroscopy

“…Recent experiments have been able to measure pure fifth-order Raman signals by suppressing the third-order cascades by careful choice of the phase matching geometry, optimized optical path length, and heterodyne detection. 42,43 In this section we will show that the contrast mechanisms that were used to suppress cascades in the fifthorder Raman-phase matching and phase-sensitive detection-do not discriminate fifth-order signal from cascades in the IR. Nevertheless, we will show that the cascading third-order signals are not a problem for the fifth-order IR experiments, in agreement with the earlier conclusion of Fulmer et al 44 because all of the transitions are allowed one quantum transitions, where fifth-order Raman has a forbidden step.…”

Two-Dimensional Infrared Spectroscopy of Photoswitchable Peptides

“…Variants of 2D vibrational spectroscopy are 2D-Raman spectroscopy (58)(59)(60) and DOVE spectroscopy (i.e., doubly vibrationally enhanced four-wave mixing, a hybrid frequency-time domain spectroscopy) (61,62). 2D spectroscopy has also been applied to electronic transitions (63)(64)(65)(66)(67)(68), addressed extensively by theoretical groups (10, [69][70][71][72][73][74][75][76][77][78][79][80][81][82], and reviewed from various perspectives (5, [83][84][85][86][87][88][89][90][91].…”