Abstract
Many recent experimental ultrafast spectroscopy studies have hinted at non-adiabatic dynamics indicating the existence of conical intersections, but their direct observation remains a challenge. The rapid change of the energy gap between the electronic states complicated their observation by requiring bandwidths of several electron volts. In this manuscript, we propose to use the combined information of different x-ray pump-probe techniques to identify the conical intersection. We theoretically study the conical intersection in pyrrole using transient x-ray absorption, time-resolved x-ray spontaneous emission, and linear off-resonant Raman spectroscopy to gather evidence of the curve crossing.
Highlights
Conical intersections (CIs),[1,2,3] though once considered rare, govern the outcome of many photochemical reactions, according to modern photochemistry.[4,5,6] They appear in a molecule when two or more potential energy surfaces (PESs) cross and enable the possibility of electronic de-excitation without radiative emission
We note that the signal shows similar features as the attosecond transient absorption spectroscopy spectrum recorded for the carbon K-edge in C2H4þ to study the conical intersection between the D0 and D1 states.[25]
A set of transient x-ray absorption spectroscopy (XAS) spectra was constructed by selecting the dominant states involved in the non-adiabatic dynamics (S0, prÃ) and the transitions to the first nitrogen 1s core hole state
Summary
Conical intersections (CIs),[1,2,3] though once considered rare, govern the outcome of many photochemical reactions, according to modern photochemistry.[4,5,6] They appear in a molecule when two or more potential energy surfaces (PESs) cross and enable the possibility of electronic de-excitation without radiative emission. These nonradiative transitions result in the breakdown of the. Ultrashort pulses with adequate resolution in both energy and time domain are required to observe them
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