A major obstacle to the gas-phase study of larger (bio)molecular systems is the vaporisation step, that is, the introduction of intact sample molecules into the gas-phase. A promising approach is the use of laser-induced acoustic desorption (LIAD) sources, which have been demonstrated using both nanosecond pulsed and continuous desorption lasers. We directly compare here both approaches for the first time under otherwise identical conditions using adenine as a prototypical biological molecule, and study the produced molecular plumes using femtosecond multiphoton ionisation. We observe different desorption mechanisms at play for the two different desorption laser sources; however, we find no evidence in either case that the desorption process leads to fragmentation of the target molecule unless excessive desorption energy is applied. This makes LIAD a powerful approach for techniques that require high density and high purity samples in the gas-phase, such as ultrafast dynamics studies or diffraction experiments.
Graphic abstract
Structural isomers,
such as conformers or tautomers, are of significant
importance across chemistry and biology, as they can have different
functionalities. In gas-phase experiments using molecular beams, formation
of many different isomers cannot be prevented, and their presence
significantly complicates the assignment of spectral lines. Current
isomer-resolved spectroscopic techniques heavily rely on theoretical
calculations or make use of elaborate double-resonance schemes. We
show here that isomer-resolved spectroscopy can also be performed
using a single tunable laser. In particular, we demonstrate single-color
isomer-resolved spectroscopy by utilizing electrostatic deflection
to spatially separate the isomers. We show that for 3-aminophenol
we can spatially separate the
syn
and
anti
conformers and use these pure samples to perform high-resolution
REMPI spectroscopy, making the assignment of transitions to a particular
isomer trivial, without any additional
a priori
information.
This approach allows one to add isomer specificity to any molecular-beam-based
experiment.
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