Ultrafast photoisomerization in DCM dye observed by new femtosecond Raman spectroscopy

Correlating the motion of electrons and nuclei with two-dimensional electronic–vibrational spectroscopy

“…Two-dimensional IR spectroscopy (2D-IR) has proved an indispensible tool for studying vibrational couplings and ground-state structures of chemical and complex biological systems (6)(7)(8). Thus far, only 1D electronicvibrational pump-probe spectroscopy, femtosecond stimulated Raman spectroscopy, and transient 2D-IR (t-2D-IR) are able to follow the evolution of nuclei on the ground or excited states subsequent to narrowband electronic excitation (9)(10)(11)(12). t-2D-IR has the unique capability of being able to study the evolution of couplings between vibrations on excited potential energy surfaces (PESs).…”

Femtosecond Studies of Solvation and Intramolecular Configurational Dynamics of Fluorophores in Liquid Solution

“…A similar conclusion was obtained recently from time-resolved stimulated Raman experiments. 135 A possible clue as to the nature of this "feeding" state are the aforementioned results of Kovalenko et al 119 who concluded from their transient absorption experiments the existence of a LE state with a characteristic time of 140 fs. Our simulation results could be improved by assuming anharmonicity in the adopted potential energy functions; especially better agreement for the time dependence of the width of the DCM emission band with the experimental data could be obtained.…”

Dependence of line shapes in femtosecond broadband stimulated Raman spectroscopy on pump-probe time delay

“…The electronic excited state dynamics of polyenes and of biological pigments have thus far been studied using time-resolved FSRS. 1,4,5,[7][8][9][10][11][12] Despite its ever increasing applications, theoretical understanding of the FSRS experiment has been formalized only recently. Early classical and quantum theories for stimulated Raman scattering were developed for cw fields, and clearly had to be modified and extended to pulsed fields.…”