Person: Bañares Morcillo, Luis
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First Name
Luis
Last Name
Bañares Morcillo
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Química Física
Area
Química Física
Identifiers
9 results
Search Results
Now showing 1 - 9 of 9
Item Contribution of resonance energy transfer to the luminescence quenching of upconversion nanoparticles with graphene oxide(Journal of Colloid and Interface Science, 2020) Méndez González, Diego; Gómez Calderón, Óscar; Melle Hernández, Sonia; González Izquierdo, Jesús; Bañares Morcillo, Luis; López Díaz, David; Velazquez Salicio, M. Mercedes; López Cabarcos, Enrique; Rubio Retama, Benito Jorge; Laurenti, MarcoUpconversion nanoparticles (UCNP) are increasingly used due to their advantages over conventional fluorophores, and their use as resonance energy transfer (RET) donors has permitted their application as biosensors when they are combined with appropriate RET acceptors such as graphene oxide (GO). However, there is a lack of knowledge about the design and influence that GO composition produces over the quenching of these nanoparticles that in turn will define their performance as sensors. In this work, we have analysed the total quenching efficiency, as well as the actual values corresponding to the RET process between UCNPs and GO sheets with three different chemical compositions. Our findings indicate that excitation and emission absorption by GO sheets are the major contributor to the observed luminescence quenching in these systems. This challenges the general assumption that UCNPs luminescence deactivation by GO is caused by RET. Furthermore, RET efficiency has been theoretically calculated by means of a semiclassical model considering the different nonradiative energy transfer rates from each Er3+ ion to the GO thin film. These theoretical results highlight the relevance of the relative positions of the Er3+ ions inside the UCNP with respect to the GO sheet in order to explain the RET-induced efficiency measurements.Item Threshold Photoelectron Spectroscopy of the CH2I, CHI, and CI Radicals(The Journal of Physical Chemistry A, 2021) Chicharro, David V.; Hrodmarsson, Helgi Rafn; Bouallagui, Aymen; Zanchet, Alexandre; Loison, Jean-Christophe; García, Gustavo A.; García Vela, Alberto; Bañares Morcillo, Luis; Marggi Poullaín, SoniaVUV photoionization of the CHnI radicals (with n = 0, 1, and 2) is investigated by means of synchrotron radiation coupled with a double imaging photoion-photoelectron coincidence spectrometer. Photoionization efficiencies and threshold photoelectron spectra (TPES) for photon energies ranging between 9.2 and 12.0 eV are reported. An adiabatic ionization energy (AIE) of 8.334 ± 0.005 eV is obtained for CH2I, which is in good agreement with previous results [8.333 ± 0.015 eV, Sztáray et al. J. Chem. Phys. 2017, 147, 013944], while for CI an AIE of 8.374 ± 0.005 eV is measured for the first time and a value of ∼8.8 eV is estimated for CHI. Ab initio calculations have been carried out for the ground state of the CH2I radical and for the ground state and excited states of the radical cation CH2I + , including potential energy curves along the C−I coordinate. Franck−Condon factors are calculated for transitions from the CH2I(X̃ 2 B1) ground state of the neutral radical to the ground state and excited states of the radical cation. The TPES measured for the CH2I radical shows several structures that correspond to the photoionization into excited states of the radical cation and are fully assigned on the basis of the calculations. The TPES obtained for the CHI is characterized by a broad structure peaking at 9.335 eV, which could be due to the photoionization from both the singlet and the triplet states and into one or more electronic states of the cation. A vibrational progression is clearly observed in the TPES for the CI radical and a frequency for the C−I stretching mode of 760 ± 60 cm−1 characterizing the CI+ electronic ground state has been extracted.Item Imaging the photodissociation dynamics of internally excited ethyl radicals from high Rydberg states(Physical Chemistry Chemical Physics, 2023) Rubio Lago, Luis; Chicharro, David V.; Marggi Poullaín, Sonia; Zanchet, Alexandre; Koumarianou, Greta; Glodic, Pavle; Samartzis, Peter C.; García Vela, Alberto; Bañares Morcillo, LuisThe site-specific hydrogen-atom elimination mechanism previously reported for photoexcited ethyl radicals (CH3CH2) [D. V. Chicharro et al., Chem. Sci., 2019, 10, 6494] is interrogated in the photodissociation of the ethyl isotopologues CD3CD2, CH3CD2 and CD3CH2 through the velocity map imaging (VMI) detection of the produced hydrogen- and deuterium-atoms. The radicals, generated in situ from photolysis of a precursor using the same laser pulse employed in their excitation to Rydberg states, decompose along the Ca-H/D and Cb-H/D reaction coordinates through coexisting statistical and site-specific mechanisms. The experiments are carried out at two excitation wavelengths, 201 and 193 nm. The comparison between both sets of results provides accurate information regarding the primary role in the site-specific mechanism of the radical internal reservoir. Importantly, at 193 nm excitation, higher energy dissociation channels (not observed at 201 nm) producing low-recoil H/Datoms become accessible. High-level ab initio calculations of potential energy curves and the corresponding non-adiabatic interactions allow us to rationalize the experimental results in terms of competitive non-adiabatic decomposition paths. Finally, the adiabatic behavior of the conical intersections in the face of several vibrational modes – the so-called vibrational promoting modes – is discussed.Item Stark control of multiphoton ionization through Freeman resonances in alkyl iodides(The Journal of Chemical Physics, 2023) Casasús, Ignacio ; Corrales, María ; Murillo Sánchez, Marta Luisa; Marggi Poullaín, Sonia; Oliveira, Nelson de; Limão-Vieira, Paulo; Bañares Morcillo, LuisMultiphoton ionization (MPI) of alkyl iodides (RI, R = CnH2n+1, n = 1–4) has been investigated with femtosecond laser pulses centered at 800 and 400 nm along with photoelectron imaging detection. In addition, the ultraviolet (UV)–vacuum ultraviolet (VUV) absorption spectra of gas-phase RIs have been measured in the photon energy range of 5–11 eV using the VUV Fourier transform spectrometer at the VUV DESIRS beamline of the synchrotron SOLEIL facility. The use of high-laser-field strengths in matter–radiation interaction generates highly non-linear phenomena, such as the Stark shift effect, which distorts the potential energy surfaces of molecules by varying both the energy of electronic and rovibrational states and their ionization energies. The Stark shift can then generate resonances between intermediate states and an integer number of laser photons of a given wavelength, which are commonly known as Freeman resonances. Here, we study how the molecular structure of linear and branched alkyl iodides affects the UV–VUV absorption spectrum, the MPI process, and the generation of Freeman resonances. The obtained results reveal a dominant resonance in the experiments at 800 nm, which counter-intuitively appears at the same photoelectron kinetic energy in the whole alkyl iodide series. The ionization pathways of this resonance strongly involve the 6p( 2 E3/2) Rydberg state with different degrees of vibrational excitation, revealing an energy compensation effect as the R-chain complexity increasesItem Wavelength dependence of the multiphoton ionization of CH3I by intense femtosecond laser pulses through Freeman resonances(Physical Chemistry Chemical Physics, 2022) Casasús, Ignacio ; Corrales, María Eugenia; Bañares Morcillo, LuisMultiphoton ionization (MPI) of methyl iodide, CH3I, has been investigated with the photoelectron imaging (PEI) technique, using high intensity femtosecond laser pulses at different central wavelengths.Item Femtochemistry under scrutiny: Clocking state-resolved channels in the photodissociation of CH3I in the A-band(The Journal of Chemical Physics, 2020) Murillo Sánchez, Marta Luisa; González Vázquez, Jesús; Corrales Castellanos, María Eugenia; Nalda Míguez, Rebeca de; Martínez Núñez, Emilio; García Vela, Alberto; Bañares Morcillo, LuisClocking of electronically and vibrationally state-resolved channels of the fast photodissociation of CH3I in the A-band is re-examined in a combined experimental and theoretical study. Experimentally, a femtosecond pump-probe scheme is employed in the modality of resonant probing by resonance enhanced multiphoton ionization (REMPI) of the methyl fragment in different vibrational states and detection through fragment velocity map ion (VMI) imaging as a function of the time delay. We revisit excitation to the center of the A-band at 268 nm and report new results for excitation to the blue of the band center at 243 nm. Theoretically, two approaches have been employed to shed light into the observations: first, a reduced dimensionality 4D nonadiabatic wavepacket calculation using the potential energy surfaces by Xie et al. [J. Phys. Chem. A 104, 1009 (2000)]; and second, a full dimension 9D trajectory surface-hopping calculation on the same potential energy surfaces, including the quantization of vibrational states of the methyl product. In addition, high level ab initio electronic structure calculations have been carried out to describe the CH3 3pz Rydberg state involved in the (2 + 1) REMPI probing process, as a function of the carbon-iodine (C–I) distance. A general qualitative agreement is obtained between experiment and theory, but the effect of methyl vibrational excitation in the umbrella mode on the clocking times is not well reproduced. The theoretical results reveal that no significant effect on the state-resolved appearance times is exerted by the nonadiabatic crossing through the conical intersection present in the first absorption band. The vibrationally state resolved clocking times observed experimentally can be rationalized when the (2 + 1) REMPI probing process is considered. None of the other probing methods applied thus far, i.e., multiphoton ionization photoelectron spectroscopy, soft X-ray inner-shell photoelectron spectroscopy, VUV single-photon ionization, and XUV core-to-valence transient absorption spectroscopy, have been able to provide quantum state-resolved (vibrational) clocking times. More experiments would be needed to disentangle the fine details in the clocking times and dissociation dynamics arising from the detection of specific quantum-states of the molecular fragments.Item Substituent effects on nonadiabatic excited state dynamics: Inertial, steric, and electronic effects in methylated butadienes(The Journal of Chemical Physics, 2020) MacDonell, Ryan ; Corrales Castellanos, María Eugenia; Boguslavskiy, Andrey ; Bañares Morcillo, Luis; Stolow, Albert; Schuurman, MichaelThe photochemical dynamics of double-bond-containing hydrocarbons is exemplified by the smallest alkenes, ethylene and butadiene. Chemical substituents can alter both decay timescales and photoproducts through a combination of inertial effects due to substituent mass, steric effects due to substituent size, and electronic (or potential) effects due to perturbative changes to the electronic potential energy surface. Here, we demonstrate the interplay of different substituent effects on 1,3-butadiene and its methylated derivatives using a combination of ab initio simulation of nonadiabatic dynamics and time-resolved photoelectron spectroscopy. The purely inertial effects of methyl substitution are simulated through the use of mass 15 “heavy-hydrogen” atoms. As expected from both inertial and electronic influences, the excited-state dynamics is dominated by pyramidalization at the unsubstituted carbon sites. Although the electronic effects of methyl group substitution are weak, they alter both decay timescales and branching ratios by influencing the initial path taken by the excited wavepacket following photoexcitation.Item From multi- to single-hollow trimetallic nanocrystals by ultrafast heating(Chemistry of Materials, 2023) Manzaneda González, Vanesa; Jenkinson, Kellie; Peña-Rodríguez, Ovidio; Borrell Grueiro, Olivia; Triviño-Sánchez, Sergio; Bañares Morcillo, Luis; Junquera González, María Elena; Espinosa, Ana; González-Rubio, Guillermo; Bals, Sara; Guerrero Martínez, AndrésMetal nanocrystals (NCs) display unique physicochemical features that are highly dependent on the nanoparticle dimensions, anisotropy, structure, and composition. The development of synthesis methodologies that allow us to tune such parameters finely emerges crucial for the application of metal NCs in catalysis, optical materials, or biomedicine. Here, we describe a synthetic methodology to fabricate hollow multimetallic heterostructures using a combination of seed-mediated growth routes and femtosecond pulsed laser irradiation. The envisaged methodology relies on the co-reduction of Ag and Pd ions on gold nanorods (Au NRs) to form Au@PdAg core–shell nanostructures containing small cavities at the Au-PdAg interface. The excitation of Au@PdAg NRs with low fluence femtosecond pulses was employed to induce the coalescence and growth of large cavities, forming multihollow anisotropic Au@PdAg nanostructures. Moreover, single-hollow alloy AuPdAg could be achieved in high yield by increasing the irradiation energy. Advanced electron microscopy techniques, energy-dispersive X-ray spectroscopy (EDX) tomography, X-ray absorption near edge structure (XANES) and FDTD (finite differences in the time domain) simulationsallowed us to characterize the morphology, structure, and elemental distribution of the irradiated NCs in detail. The ability of the reported synthesis route to fabricate multimetallic NCs with unprecedented hollow nanostructures brings attractive prospects for the fabrication of tailored high-entropy alloy nanoparticles.Item Site-specific hydrogen-atom elimination in photoexcited alkyl radicals(Physical Chemistry Chemical Physics, 2021) Chicharro Vacas, David; Zanchet, Alexandre; Bouallagui, Aymen; Rubio-Lago, Luis; García-Vela, Alberto; Bañares Morcillo, Luis; Marggi Poullaín, SoniaA prompt site-specific hydrogen-atom elimination from the α-carbon atom (Cα) has been recently reported to occur in the photodissociation of ethyl radicals following excitation at 201 nm [Chicharro et al., Chem. Sci., 2019, 10, 6494]. Such pathway was accessed by means of an initial ro-vibrational energy characterizing the radicals produced by in situ photolysis of a precursor. Here, we present experimental evidence of a similar dynamics in a series of alkyl radicals (C2H5, n-C3H7, n-C4H9, and i-C3H7) containing the same reaction coordinate, but different extended structures. The main requirements for the site-specific mechanism in the studied radicals, namely a rather high content of internal energy prior to dissociation and the participation of vibrational promoting modes, is discussed in terms of the chemical structure of the radicals. The methyl deformation mode in all alkyl radicals along with the CH bending motion in i-C3H7 appear to promote this fast H-atom elimination channel. The photodissociation dynamics of the simplest unsaturated alkyl radical, the vinyl radical (C2H3), is also discussed, showing no signal of site-specific fast H-atom elimination. The results are complemented with high-level ab initio electronic structure calculations of potential energy curves of the vinyl radical, which are compared with those previously reported for the ethyl radical.