Probing competing relaxation pathways in malonaldehyde with transient X-ray absorption spectroscopy.

Chemical Science
Nanna Holmgaard ListTodd J Martínez

Abstract

Excited-state intramolecular hydrogen transfer (ESIHT) is a fundamental reaction relevant to chemistry and biology. Malonaldehyde is the simplest example of ESIHT, yet only little is known experimentally about its excited-state dynamics. Several competing relaxation pathways have been proposed, including internal conversion mediated by ESIHT and C[double bond, length as m-dash]C torsional motion as well as intersystem crossing. We perform an in silico transient X-ray absorption spectroscopy (TRXAS) experiment at the oxygen K-edge to investigate its potential to monitor the proposed ultrafast decay pathways in malonaldehyde upon photoexcitation to its bright S2(ππ*) state. We employ both restricted active space perturbation theory and algebraic-diagrammatic construction for the polarization propagator along interpolated reaction coordinates as well as representative trajectories from ab initio multiple spawning simulations to compute the TRXAS signals from the lowest valence states. Our study suggests that oxygen K-edge TRXAS can distinctly fingerprint the passage through the H-transfer intersection and the concomitant population transfer to the S1(nπ*) state. Potential intersystem crossing to T1(ππ*) is detectable from reappear...Continue Reading

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Citations

Jun 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Ibon AlkortaJanet E Del Bene
Feb 6, 2021·Journal of Chemical Theory and Computation·Thomas FranssonAndreas Dreuw
Feb 11, 2021·Faraday Discussions·Thomas J A WolfMarkus Gühr
Mar 18, 2021·The Journal of Physical Chemistry. a·C D Rankine, T J Penfold

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Methods Mentioned

BETA
X-ray

Software Mentioned

CVS
Bagel
OpenMolcas
TRXAS
AIMS
ADC
LIBWFA
Chem
RASPT2
XMS

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