4 research outputs found
Effect of cluster environment on the electron attachment to 2-nitrophenol
Effect of cluster environment on the electron attachment to 2-nitrophenol (2NP) is
studied in homogeneous 2NP clusters and heterogeneous clusters of 2NP, argon and water.
The cluster environment significantly reduces fragmentation of 2NP after electron
attachment. Parent cluster anions 2NPn- are primary reaction
products in both, homogeneous and heterogeneous clusters. Non-dissociative electron
attachment to homogeneous clusters proceeds at low energies <2 eV, presumably via dipole-supported
states. In heterogeneous clusters, the interaction with low energy (<2 eV) electrons is shielded by the
solvent. Surprisingly, the energetic threshold for the electron attachment rises with the
number (n) of
2NP molecules in the cluster (2NP)n-. This rise can be either due to
a strong change of the 2NP conformation induced by the cluster environment or due to the
the competition with electron autodetachment after proton transfer that has been first
observed by Allan in the formic acid dimer [M. Allan, Phys. Rev. Lett. 98,
123201 (2007)]. We observe the same threshold rise for complex Arm·(2NP)n- and
H2O·(2NP)n- anions. This indicates that the
electron attachment to 2-nitrophenol in cluster environment is more influenced by the
solute − solute interaction
compared to the solute − solvent interaction
Vibrationally mediated photodissociation dynamics of pyrrole
We investigate photodissociation of vibrationally excited pyrrole molecules in a velocity map imaging experiment with IR excitation of N–H bond stretching vibration v1 = 1, νIR= 3532 cm−1, and UV photodissociation at λUV= 243 nm. In the IR+UV experiment, the H-fragment signal is enhanced with respect to the 243 nm UV-only photodissociation due to a more favorable Franck-Condon factor for the vibrationally excited molecule. In the measured H-fragment kinetic energy distribution, the maximum of the fast peak in the IR+UV experiment is shifted by 0.23 eV compared to the UV-only photodissociation which corresponds to 53 % of the vibrational energy deposited into the fragment kinetic energy. We compare our results with an isoenergetic UV-only photodissociation at λUV= 224 nm. About 72 % of the total available energy, is released into the fragment kinetic energy in the IR+UV experiment, while it is only 61 % in the UV-only photodissociation. This can be substantiated by the coupling of the N–H bond stretching vibration into the kinetic energy of the departing H-fragment. We also probe the time-dependent dynamics by a nanosecond pump-probe experiment. The IR excitation enhances the N–H bond dissociation even when the UV photodissociation is delayed by 150 ns. This enhancement increases also the yield of the fast fragments at the position of the peak corresponding to the IR+UV excitation, i.e. even 150 ns after the IR vibrational excitation, the same amount of the IR excitation energy can be converted into the H-fragment velocity as immediately after the excitation
Photochemistry of Nitrophenol Molecules and Clusters: Intra- vs Intermolecular Hydrogen Bond Dynamics
We investigate both experimentally
and theoretically the structure
and photodynamics of nitrophenol molecules and clusters, addressing
the question how the molecular photodynamics can be controlled by
specific inter- and intramolecular interactions. Using quantum chemical
calculations, we demonstrate the structural and energetic differences
between clusters of 2-nitrophenol and 4-nitrophenol, using phenol
as a reference system. The calculated structures are supported by
mass spectrometry. The mass spectra of 2-nitrophenol clusters provide
an evidence for a stacked structure compared to a strong O–H···O
hydrogen bonding for 4-nitrophenol aggregates. We further investigate
the photodynamics of nitrophenol molecules and clusters by means of
velocity map imaging of the H-fragment generated upon 243 nm photodissociation.
The experiments are complemented by <i>ab initio</i> calculations
which demonstrate distinct photophysics of phenol, 2-nitrophenol,
4-nitrophenol. The measured H-fragment kinetic energy distributions
(KEDs) from 2-nitrophenol molecules are compared to the KEDs from
phenol. The comparison points to the intramolecular O–H···O
hydrogen bond in 2‑nitrophenol, stimulating fast internal conversion
into the ground electronic state. This reaction channel is marked
by exclusive appearance of slow statistical hydrogen fragments in
2-nitrophenol, which contrasts with fast hydrogen atoms observed for
phenol. The photodissociation of 2-nitrophenol clusters yields a fraction
of H-fragments with higher kinetic energies than the isolated molecules.
These fragments originate from the caging effect in the clusters leading
to multiphoton dissociation of molecules excited by the previous photons.
We also propose a new <i>ab initio</i> based value for the
O–H bond dissociation enthalpy in 2-nitrophenol (4.25 eV),
which is in excellent agreement with the maximum measured H-fragment
kinetic energy
Decomposition of Iron Pentacarbonyl Induced by Singly and Multiply Charged Ions and Implications for Focused Ion Beam-Induced Deposition
International audienceFocused ion beams are becoming important tools in nanofabrication.The underlying physical processes in the substrate were already explored for severalprojectile ions. However, studies of ion interaction with precursor molecules forbeam-assisted deposition are almost nonexistent. Here, we explore the interaction ofvarious projectile ions with iron pentacarbonyl. We report fragmentation patterns ofisolated gas-phase iron pentacarbonyl after interaction with 4He+ at a collisionenergy of 16 keV, 4He2+ at 16 keV, 20Ne+ at 6 keV, 20Ne4+ at 40 keV, 40Ar+ at 3 keV,40Ar3+ at 21 keV, 84Kr3+ at 12 keV, and 84Kr17+ at 255 keV. These projectiles coverinteraction regimes ranging from collisions dominated by nuclear stopping throughcollisions dominated by electronic stopping to soft resonant electron-captureinteractions. We report a surprising efficiency of Ne+ in the Fe(CO)5decomposition. The interaction with multiply charged ions results in a highercontent of parent ions and slow metastable fragmentation due to the electroncaptureprocess. The release of CO groups during the decomposition process seems to take off a significant amount of energy.The fragmentation mechanism may be described as Fe being trapped within a CO cluster