Internal conversion | EPFL Graph Search

Internal conversion is an atomic decay process where an excited nucleus interacts electromagnetically with one of the orbital electrons of an atom. This causes the electron to be emitted (ejected) from the atom. Thus, in internal conversion (often abbreviated IC), a high-energy electron is emitted from the excited atom, but not from the nucleus. For this reason, the high-speed electrons resulting from internal conversion are not called beta particles, since the latter come from beta decay, where they are newly created in the nuclear decay process. IC is possible whenever gamma decay is possible, except if the atom is fully ionized. In IC, the atomic number does not change, and thus there is no transmutation of one element to another. Since an electron is lost from the atom, a hole appears in an electron shell which is subsequently filled by other electrons that descend to that empty, lower energy level, and in the process emit characteristic X-ray(s), Auger electron(s), or both. The

Ultrafast Photoelectron and Optical Spectroscopies of Photoinduced Processes in Molecular Systems in Solution

Luca Longetti

Investigating molecular excitations with femtosecond time resolution is of pivotal importance to understand the out-of-equilibrium processes taking place in molecular systems upon light absorption. The photochemistry of solvated species is heavily determined by the early steps of the relaxation dynamics. In this thesis, ultrafast electronic spectroscopies are exploited to study relaxation dynamics of photoexcited molecules in solution by probing the transient electronic structure. Vacuum-ultraviolet (VUV) ultrashort monochromatized light pulses (HARMONIUM, 15-100 eV) are exploited for steady-state photoelectron spectroscopy (PES) and time-resolved PES in a pump-probe scheme. This is a powerful tool for investigating electronic structure and ultrafast processes of solvated molecules with high time (50fs) and energy (0.12eV) resolution. PES retrieves binding energies of valence and core electronic states with elemental specificity and without the constraints of selection rules, and is here applied to liquids and solutions by means of a liquid micro-jet. With the aim of extending this technique to a larger class of solutes, we demonstrate the capability to perform studies on volatile liquids such as organic solvents. PES spectra of gas phase and liquid phase aromatic compounds are presented and their valence orbitals are compared and identified. The solvation is discussed and the vertical ionization energies are reported. This retrieves important parameters for electrochemistry and opens new perspectives towards PES studies of molecules in organic solvents. Upon photoexcitation, molecules can undergo several relaxation processes such as nonradiative relaxation processes which include dissociation, internal conversion and intersystem crossing. Energy can also be released to the solvent environment by intermolecular processes such as vibrational energy transfer. All of these phenomena are reflected in a transient electronic configuration. PES can hence probe electronic and structural dynamics along the entire reaction coordinates. The ferric trisoxalate complex represents an ideal coordination compound showing an intriguing cascade of processes upon photoexcitation. We have directly observed the metal photoreduction due to an instantaneous intramolecular charge transfer. We then suggest a branching between photodissociation and a back-electron transfer channels, which completes the picture of the compoundâs photochemistry. This experiment shows PES sensitivity to oxidation state changes, providing an interesting perspective for photoredox reaction studies in solution and for intra- and inter-molecular charge-transfer phenomena. Vibrational wave packets (WP) are interesting observables to map non-adiabatic dynamics, relaxation pathways and coupling to solvent of the excited molecule. We have investigated molecular iodine in ethanol, which we have studied first by optical transient absorption spectroscopy using a white light continuum probe. The electronic absorption spectrum of I2 in ethanol is strongly modified compared to the case of other organic solvents, due to a strong coupling of covalent and ionic states. We have mapped the vibrational WP dynamics, in particular its trajectory and damping along the I-I bond axis. This study is intended to prepare for an ultrafast PES experiment aimed at linking the response of inner shells to the WP launched in the valence states. Preliminary steady-state PES spectra are reported and discussed.

EPFL2020

Development and validation of a double focalizing magnetic spectrometer for beta spectrum measurements

François Bochud, Guido Haefeli

In the framework of the EMPIR project MetroBeta, the development and optimization of a double focalizing magnetic spectrometer have been realized in order to measure the beta spectra shape. The acquisition is designed to perform, after focalization by the magnetic field, an energy selection using a window on the deposited energy in the Si detector. The energy calibration is performed using conversion electrons from Cd-109, Cs-137, Ba-133 and Bi-207 and the measured energy resolution is 1.3% at 1 MeV. The efficiency is measured experimentally using a Tl-204 source and is used to reconstruct the spectrum shape for beta emitters with end-point energy up to 750 keV. Two beta emitters with allowed transitions, Cs-134 and Co-60, are used to validate the measurement and the reconstruction method. Finally the measurement of the beta shape of Cl-36, a non-unique 2nd forbidden transition is presented.

ELSEVIER2019

Multiple Charge Transfer States in Donor-Acceptor Heterojunctions with Large Frontier Orbital Energy Offsets

Xiao Liu, Björn Niesen, Chien-Jen Yang

In this work, we demonstrate several organic amorphous donor-acceptor systems that exhibit sub-bandgap features over a more than 2 eV spectral range. An in-depth study of one of these systems, NPB:HAT-CN (NPB is N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine and HAT-CN is 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile), reveals that the broad sub-bandgap features are attributed to multiple electronic charge transfer (CT) state transitions, broadened by energetic disorder sourcing from the fluctuations of intramolecular conformations and by the disordered intermolecular environment. These unique CT features originate from an unconventional donor and acceptor selection that reveals new insight about photocurrent generation and nonradiative recombination. Unlike materials employed in high performing organic solar cells, the materials studied here feature large optical energy gaps with very large frontier orbital energy level offsets, creating high bandgap devices with low open-circuit voltage. In addition to multiple electronic CT levels, we reveal that the internal quantum efficiency of these multiple CT transitions is not constant but photon energy dependent and with photoluminescence that originates primarily from the second lowest electronic CT state implying slow (relative to radiative and nonradiative rates) internal conversion within the CT manifold. Overall, this class of donor-acceptor pairs provides an opportunity to probe CT states in unique ways to potentially unravel their role in carrier generation-recombination and energy loss mechanisms.

2019

Ultrafast Photoelectron and Optical Spectroscopies of Photoinduced Processes in Molecular Systems in Solution

Luca Longetti

EPFL2020