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A New Strategy for Vibronic Spectroscopy of Radicals

Project description

Characterizing radicals with high resolution vibronic spectroscopy

Free radicals are reactive molecules with unpaired electrons. This open shell electronic configuration makes them notoriously difficult to study. As reactive intermediates, they are usually short lived and very seldom isolated, and their quantum mechanical behavior is challenging. The EU-funded RadSpec project aims to provide answers to longstanding questions about the quantum mechanical and chemical behavior of both known and unknown reactive intermediates using vibronic spectroscopy methods. Project results are expected to significantly impact on a number of fields including combustion, atmospheric chemistry, polymerisation, plasma chemistry, biochemistry, and many other chemical processes.


This proposal aims to develop a novel strategy for high resolution vibronic spectroscopy of radicals, with
unprecedented sensitivity, specificity, and applicability. The proposed scheme will provide answers to
longstanding quantum mechanical questions about non-adiabatic dynamics, and, in combination with a
unique, recently developed transparent microreactor source of reactive molecules, enable the pursuit of
unknown reactive intermediates.
Radicals and transient reactive intermediates are centrally important to chemistry but notoriously difficult
to study. The proposer has recently led several successful experimental and theoretical efforts directed
at molecules and transition states thought to be extremely difficult if not impossible to characterize. Here
we propose to launch a revolutionary approach to spectroscopy of these important species, exploiting a
key insight into dissociation dynamics on top of elements of state of the art laser spectroscopy techniques
in the infrared, ultraviolet, and vacuum ultraviolet to forge a new universal method. It possesses the high
sensitivity and mass selectivity of ion detection, while simultaneously being multidimensional and fully
rovibronic in scope to extract the maximum possible information about coupled nuclear and electronic
We anticipate that this advance will also be of great interest and utility to a broad swath of researchers
in related fields, such as combustion, atmospheric chemistry, and surface science, who require the ability
to track rare but reactive species. The nitrate and cyclopentadienyl radicals will initially be targeted as
particularly important examples, and we also plan to hunt for as yet unobserved reactive intermediates
using our new spectroscopic scheme alongside the flexibility of our molecular source to rationally explore
chemical phase space.

Host institution

Net EU contribution
€ 1 687 500,00
Total cost
€ 1 687 500,00

Beneficiaries (1)