Issue 3, 2022

Electronic relaxation and dissociation dynamics in formaldehyde: pump wavelength dependence

Abstract

The effect of the incident UV pump wavelength on the subsequent excited state dynamics, electronic relaxation, and ultimate dissociation of formaldehyde is studied using first principles simulation and Coulomb explosion imaging (CEI) experiments. Transitions in a vibronic progression in the Ã[X with combining tilde] absorption band are systematically prepared using a tunable UV source which generates pulses centered at 304, 314, 329, and 337 nm. We find, both via ab initio simulation and experimental results, that the rate of excited state decay and subsequent dissociation displays a prominent dependence on which vibronic transition in the absorption band is prepared by the pump. Our simulations predict that nonadiabatic transition rates and dissociation yields will increase by a factor of >100 as the pump wavelength is decreased from 337 to 304 nm. The experimental results and theoretical simulations are in broad agreement and both indicate that the dissociation rate plateaus rapidly after ≈2 ps following an ultrafast sub-ps rise.

Graphical abstract: Electronic relaxation and dissociation dynamics in formaldehyde: pump wavelength dependence

Article information

Article type
Paper
Submitted
18 set 2021
Accepted
10 dez 2021
First published
14 dez 2021

Phys. Chem. Chem. Phys., 2022,24, 1779-1786

Electronic relaxation and dissociation dynamics in formaldehyde: pump wavelength dependence

T. Endo, S. P. Neville, P. Lassonde, C. Qu, H. Fujise, M. Fushitani, A. Hishikawa, P. L. Houston, J. M. Bowman, F. Légaré, M. S. Schuurman and H. Ibrahim, Phys. Chem. Chem. Phys., 2022, 24, 1779 DOI: 10.1039/D1CP04264E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements