Femtosecond infrared coherent excitation of liquid phase vibrational population distributions (v>5)

Fully absorptive 3D IR spectroscopy using a dual mid-infrared pulse shaper

“…The time delay between the two pump pulses and the probe pulse are controlled by a Newport automatic translation stage. The metal carbonyls, W(CO) 6 and RDC, were purchased from Sigma Aldrich and used without further purification. The samples were dissolved in hexane to yield an OD of 0.4, which is in millimolar concentration range.…”

“…Such phase relationship is expected from the extra factor of i 2 in the perturbative expansion of the density matrix 54 and agrees with previous observations. 9,56 B. W(CO) 6 /hexane W(CO) 6 has six CO stretching modes. However in a symmetric environment, it has only one triply degenerate IR active mode T 1u and thus can be considered to be a single oscillator system.…”

“…These compounds have very strong infrared absorption coefficients, long population and coherence times, and have mostly homogeneous dynamics, and so are often used as model systems in nonlinear IR spectroscopy. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] W(CO) 6 has a single carbonyl absorption band, while RDC has two coupled modes. 3D IR spectra are collected in both the time-and frequency-domains so as to understand the effects of pulse convolution.…”

“…We demonstrate our 3D IR approach on two metalcarbonyl compounds, W(CO) 6 and dicarbonylacetylacetonato rhodium (I) (RDC). These compounds have very strong infrared absorption coefficients, long population and coherence times, and have mostly homogeneous dynamics, and so are often used as model systems in nonlinear IR spectroscopy.…”

“…4 With 2D IR spectroscopy now well developed, attention is turning to 3D and higher correlations. [5][6][7][8][9] Analogous to how peaks are spread into a plane in 2D IR spectroscopy; the planes will be spread over a cube in 3D IR spectra. A 3D spectrum can be generated in a number of different ways.…”