References of "Physical Chemistry Chemical Physics [=PCCP]"
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See detailLight and oxygen induce chain scission of conjugated polymers in solution
Caubergh, Stéphane ULiege; Louis, Boris; Larsson, Per-Olof et al

in Physical Chemistry Chemical Physics [=PCCP] (2017)

Conjugated polymers have been widely studied as flexible, versatile semiconductors in organic electronics. However, the material stability is one of the problems limiting their applications. Thus ... [more ▼]

Conjugated polymers have been widely studied as flexible, versatile semiconductors in organic electronics. However, the material stability is one of the problems limiting their applications. Thus, understanding the degradation process of conjugated polymers is crucial. In this work, we monitored the chain scission of the model polymer MEH-PPV in solutions under different conditions by assessing its molecular weight using Gel permeation chromatography and optical spectral measurements. We showed that changes in the UV-VIS spectrum can be seen only when the degradation has already progressed substantially. Fluorescence spectrum was found to be almost totally insensitive to the degradation stage of the polymers. We demonstrate that chain scission in solutions happens even in the dark leading to a decrease of about 15% of the molecular weight after just one day of storage. If exposed to room-light, the chain length decreases about 10 times over one day of exposure. Using stronger light intensity or enriching the solution with oxygen accelerates the degradation process dramatically. The rate of the reaction follows approximately a square root dependence with light intensity and oxygen concentration. We conclude that some extent of polymer degradation is difficult to avoid in common laboratory practices since to prevent it one needs to work in oxygen free atmosphere in the dark. Preparation of polymer films from partially degraded solutions might lead not only to losing the connection between the molecular weight and the opto-electronic properties but also to unintentional doping of the semiconductor by products of chains scission reactions. [less ▲]

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See detailCoherent electronic and nuclear dynamics in a rhodamine heterodimer-DNA supramolecular complex
Cipolloni, M.; Fresch, B.; Occhiuto, I. et al

in Physical Chemistry Chemical Physics [=PCCP] (2017), 19(34), 23043-23051

Elucidating the role of quantum coherences in energy migration within biological and artificial multichromophoric antenna systems is the subject of an intense debate. It is also a practical matter because ... [more ▼]

Elucidating the role of quantum coherences in energy migration within biological and artificial multichromophoric antenna systems is the subject of an intense debate. It is also a practical matter because of the decisive implications for understanding the biological processes and engineering artificial materials for solar energy harvesting. A supramolecular rhodamine heterodimer on a DNA scaffold was suitably engineered to mimic the basic donor-acceptor unit of light-harvesting antennas. Ultrafast 2D electronic spectroscopic measurements allowed identifying clear features attributable to a coherent superposition of dimer electronic and vibrational states contributing to the coherent electronic charge beating between the donor and the acceptor. The frequency of electronic charge beating is found to be 970 cm-1 (34 fs) and can be observed for 150 fs. Through the support of high level ab initio TD-DFT computations of the entire dimer, we established that the vibrational modes preferentially optically accessed do not drive subsequent coupling between the electronic states on the 600 fs of the experiment. It was thereby possible to characterize the time scales of the early time femtosecond dynamics of the electronic coherence built by the optical excitation in a large rigid supramolecular system at a room temperature in solution. © 2017 the Owner Societies. [less ▲]

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See detailLow-lying, Rydberg states of polycyclic aromatic hydrocarbons (PAHs) and cyclic alkanes
Bohl, E.; Mignolet, Benoît ULiege; Johansson, J. O. et al

in Physical Chemistry Chemical Physics [=PCCP] (2017), 19(35), 24090-24099

TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions ... [more ▼]

TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small "hollow" carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules. © 2017 the Owner Societies. [less ▲]

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See detailPumping and probing vibrational modulated coupled electronic coherence in HCN using short UV fs laser pulses: A 2D quantum nuclear dynamical study
van den Wildenberg, Stéphan ULiege; Mignolet, Benoît ULiege; Levine, R. D. et al

in Physical Chemistry Chemical Physics [=PCCP] (2017), 19(30), 19837-19846

The coupled electronic-nuclear coherent dynamics induced by a short strong VUV fs pulse in the low excited electronic states of HCN is probed by transient absorption spectroscopy with a second weaker fs ... [more ▼]

The coupled electronic-nuclear coherent dynamics induced by a short strong VUV fs pulse in the low excited electronic states of HCN is probed by transient absorption spectroscopy with a second weaker fs UV pulse. The nuclear time-dependent Schrodinger equation is solved on a 2D nuclear grid with several electronic states with a Hamiltonian including the dipole coupling to the pump and the probe electric fields. The two internal nuclear coordinates describe the motion of the light H atom. There is a band of several excited electronic states at about 8 eV above the ground state (GS) that is transiently accessed by the pump pulse. We tailored the pump so as to selectively populate the lowest 1A′′ electronic state thereby the pulse creates an electronic coherence with the GS. Our simulations show that this electronic coherence is modulated by the nuclear motion and persists all the way to dissociation on the 1A′′ state. Transient absorption spectra computed as a function of the delay time between the pump and the probe pulses provide a detailed probe of the electronic amplitude and its phase, as well as of the modulation of the electronic coherence by the nuclear motion, both bound and dissociative. © the Owner Societies 2017. [less ▲]

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See detailSupramolecular influence on cis–trans isomerization probed by ion mobility spectrometry
Czerwinska, Izabella; Kulesza, Alexander; Choi, Changmin et al

in Physical Chemistry Chemical Physics [=PCCP] (2016), 18

We used tandem ion mobility spectrometry measurements to investigate how the photo-isomerization of a chromophore (a methylpyridinium derivative) is affected by the complexation with a crown ether. A ... [more ▼]

We used tandem ion mobility spectrometry measurements to investigate how the photo-isomerization of a chromophore (a methylpyridinium derivative) is affected by the complexation with a crown ether. A dramatic blue-shift of the photo-isomerization spectrum was observed upon complexation, which could be well reproduced by ab initio calculations. Our results support that the observed changes in the photo-physical properties of the chromophore originate from the charge-solvation of its pyridinium moiety by the host cage. [less ▲]

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See detailQuantum effects in ultrafast electron transfers in cytochrome
Firmino, Thiago; Mangaud, Etienne; Cailliez, Fabien et al

in Physical Chemistry Chemical Physics [=PCCP] (2016), 18

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See detailAtomistic account of structural and dynamical changes induced by small binders in the double helix of a short DNA
Fresch, Barbara ULiege; Remacle, Françoise ULiege

in Physical Chemistry Chemical Physics [=PCCP] (2014), 16

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See detailMulti-scale modeling of mycosubtilin lipopeptides at the air/water interface: structure and optical second harmonic generation
Loison, Claire; Nasir, Mehmet Nail ULiege; Benichou, Emmanuel et al

in Physical Chemistry Chemical Physics [=PCCP] (2014), 16

Monolayers of the lipopeptide mycosubtilin are studied at the air/water interface. Their structure is investigated using molecular dynamics simulations. All-atom models suggest that the lipopeptide is ... [more ▼]

Monolayers of the lipopeptide mycosubtilin are studied at the air/water interface. Their structure is investigated using molecular dynamics simulations. All-atom models suggest that the lipopeptide is flexible and aggregates at the interface. To achieve simulation times of several microseconds, a coarse-grained (CG) model based on the MARTINI force field was also used. These CG simulations describe the formation of half-micelles at the interface for surface densities up to 1 lipopeptide per nm2. In these aggregates, the tyrosine side chain orientation is found to be constrained: on average, its main axis, as defined along the C–OH bond, aligns along the interface normal and points towards the air side. The origin of the optical second harmonic generation (SHG) from mycosubtilin monolayers at the air/water interface is also investigated. The molecular hyperpolarizability of the lipopeptide is obtained from quantum chemistry calculations. The tyrosine side chain contribution to the hyperpolarizability is found to be dominant. The orientation distribution of tyrosine, associated with a dominant hyperpolarizability component along the C–OH bond of the tyrosine, yields a ratio of the susceptibility elements χ(2)ZZZ/χ(2)ZXX consistent with the experimental measurements recently reported by M. N. Nasir et al. [Phys. Chem. Chem. Phys., 2013, 15, 19919]. [less ▲]

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See detailInfluence of the tyrosine environment on the second harmonic generation of iturinic antimicrobial lipopeptides at the air–water interface
Nasir, Mehmet Nail ULiege; Benichou, Emmanuel; Loison, Claire et al

in Physical Chemistry Chemical Physics [=PCCP] (2013), 15

The second harmonic generation (SHG) response at the air–water interface from the tyrosine-containing natural iturinic cyclo-lipopeptides mycosubtilin, iturin A and bacillomycin D is reported. It is shown ... [more ▼]

The second harmonic generation (SHG) response at the air–water interface from the tyrosine-containing natural iturinic cyclo-lipopeptides mycosubtilin, iturin A and bacillomycin D is reported. It is shown that this response is dominated by the single tyrosine residue present in these molecules owing to the large first hyperpolarizability arising from the non-centrosymmetric aromatic ring structure of this amino acid. The SHG response of these iturinic antibiotics is also compared to the response of surfactin, a cyclo-lipopeptide with a similar L,D-amino acid sequence but lacking a tyrosine residue, and PalmATA, a synthetic linear lipopeptide possessing a single tyrosine residue but lacking the amino acid sequence structuring the cycle of the iturinic antibiotics. From the light polarization analysis of the SHG response, it is shown that the tyrosine local environment is critical in defining the SHG response of these peptides at the air–water interface. Our results demonstrate that tyrosine, similar to tryptophan, can be used as an endogenous molecular probe of peptides and proteins for SHG at the air–water interface, paving the way for SHG studies of other tyrosine-containing bioactive molecules. [less ▲]

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See detailMorphological and opto-electrical properties of solution deposited Platinum counter electrode for low cost dye sensitized solar cells
Thalluri, Venkata Visveswara Gopala Kris ULiege; Décultot, Marc ULiege; Henrist, Catherine ULiege et al

in Physical Chemistry Chemical Physics [=PCCP] (2013), 15

Although Platinum (Pt) is a rare and very expensive material, Pt counter electrodes are still very commonly used for reaching high efficiencies in dye-sensitized solar cells (DSCs). The use of alternative ... [more ▼]

Although Platinum (Pt) is a rare and very expensive material, Pt counter electrodes are still very commonly used for reaching high efficiencies in dye-sensitized solar cells (DSCs). The use of alternative cheaper catalyst materials did not yet yield to equivalent efficiencies. In this work, we tried to understand how to reduce the amount of deposited Pt-material and simultaneously to deliver higher DSC performances. We systematically compared the properties of Pt-counter electrodes prepared by simple solution deposition methods such as spray-coating, dip-coating, brushing with reference to the Pt-electrodes prepared by sputtering onto fluorine doped-tin oxides (FTOs). The morphological and structural characterizations of the deposited Pt-layers were performed by atomic force microscopy (AFM) and scanning electron microscope (SEM). The composition of Pt-material was quantified by using SEM electron dispersive x-ray (EDX) mapping measurements are further compared with optical transmission measurements. Also contact angle and sheet resistance measurements were performed. By taking Pt-layers composition, morphology and structural factors into account 9.16% efficient N3 dye based DSCs were assembled. The DSCs were subjected to various opto-electrical characterization techniques like current-voltage (I-V), external quantum efficiency (EQE), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and transient photo voltage (TPV) measurements. The obtained experimental data suggest that the Pt counter electrodes prepared by solution deposition methods can also reach to high DSC device performances with a consumption of very less amount of Pt material compared with sputtered Pt-layers. This process also proves that higher DSC performances are not limited to the usage of sputtered Pt-layer as counter electrode. [less ▲]

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See detailBubble bouncing at a clean water surface
zawala, jan; Dorbolo, Stéphane ULiege; Vandewalle, Nicolas ULiege et al

in Physical Chemistry Chemical Physics [=PCCP] (2013), 15

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See detailCharacterization of the MgO2+ dication in the gas phase: electronic states, spectroscopy and atmospheric implications
Linguerri, Roberto; Hochlaf, Majdi; Baccus-Montabonel, Marie-Christine et al

in Physical Chemistry Chemical Physics [=PCCP] (2013), 15(3), 824-831

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See detailMonolayer Properties of Uronic Acid Bicatenary Derivatives at the Air-Water Interface: Effect of Hydroxyl Group Stereochemistry Evidenced by Experimental and Computational Approaches
Razafindralambo, Hary ULiege; Richel, Aurore ULiege; Wathelet, Bernard ULiege et al

in Physical Chemistry Chemical Physics [=PCCP] (2011), 13(33), 1529115298

By screening uronic acid-based surfactant interfacial properties, the effect of the hydroxyl group stereochemistry (OH-4) on the conformation of bicatenary (disubstituted) derivatives at the air–water ... [more ▼]

By screening uronic acid-based surfactant interfacial properties, the effect of the hydroxyl group stereochemistry (OH-4) on the conformation of bicatenary (disubstituted) derivatives at the air–water interface has been evidenced by experimental and computational approaches. Physical and optical properties of a monolayer characterized by Langmuirfilmbalance, Brewster angle microscopy, and ellipsometry at 20°C reveal that the derivative of glucuronate (C14/14–GlcA) forms a more expanded monolayer, and shows a transition state under compression, in the opposite to that of galacturonate (C14/14–GalA). Both films are very mechanically resistant (compression modulus > 300m Nm-1) and stable (collapse pressure exceeding 60mNm-1), while that of C14/14–GalA exhibits a very high compression modulus up to 600mNm-1 like films in the solid state. Computational approaches provide single and assembly molecular models that corroborate the molecule expansion degree and interactions data from experimental results. Differences in the molecular conformation and film behaviours of uronic acid bicatenary derivatives at the air–water interface are attributed to the intra-H-bonding formation, which is more favourable with an OH-4 in the axial (C14/14–GalA) than in the equatorial position (C14/14–GlcA). [less ▲]

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See detailStereocontrol of attosecond time-scale electron dynamics in ABCU using ultrafast laser pulses: a computational study
Mignolet, Benoît ULiege; Gijsbertsen, A.; Vrakking, M. J. J. et al

in Physical Chemistry Chemical Physics [=PCCP] (2011), 13(18), 8331-8344

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See detailImplementing quantum algorithms in hyperfine levels of ultracold polar molecules by optimal control
Pellegrini, Philippe; Vranckx, Stéphane; Desouter, Michèle ULiege

in Physical Chemistry Chemical Physics [=PCCP] (2011), 13

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See detailLiMSO(4)F (M = Fe, Co and Ni): promising new positive electrode materials through the DFT microscope
Frayret, Christine; Villesuzanne, Antoine; Spaldin, Nicola et al

in Physical Chemistry Chemical Physics [=PCCP] (2010), 12(47), 15512-15522

A theoretical study of the lithium intercalated LiMSO(4)F and deintercalated MSO(4)F systems, where M = Fe, Co and Ni has been performed within the framework of density functional theory. Beyond ... [more ▼]

A theoretical study of the lithium intercalated LiMSO(4)F and deintercalated MSO(4)F systems, where M = Fe, Co and Ni has been performed within the framework of density functional theory. Beyond predictions of structural evolution and average voltages versus a lithium electrode, we have applied partial density of states and Bader's topological analysis of the electron density to the study of lithium deintercalation. Upon lithium extraction, charge rearrangement occurs for nickel between different d-orbitals, but with little net positive charge gain, while cobalt and iron atoms end up with a clear oxidized state. The participation of oxygen ions in accepting the electron of the lithium is thus enhanced for LiNiSO(4)F. However, this effect does not affect the long-range electrostatic interactions a lot in the lithiated phase, since the valence of all transition metals is very close due to initial lower oxidized state for the Ni atom in the host. It is found that this is not essentially a long-range electrostatic interaction within the lithiated phase but within the host which explains, at least partly, the increase in voltage by passing from Fe to Ni. Our results also shed light upon the possibility of getting an approximate evaluation of the local strain associated with delithiation from the atomic volume evolutions, which are also likely to affect the electrochemical potential. [less ▲]

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See detailControlled full adder-subtractor by vibrational computing
Bomble, L.; Lauvergnat, D.; Remacle, Françoise ULiege et al

in Physical Chemistry Chemical Physics [=PCCP] (2010), 12(48), 15628-15635

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See detailFirst-principles study of the dynamical and nonlinear optical properties of urea single crystals
Hermet, Patrick ULiege; Ghosez, Philippe ULiege

in Physical Chemistry Chemical Physics [=PCCP] (2010), 12

Raman and infrared spectra of urea single crystals have been calculated using the density functional theory. This allowed us to assign the remaining experimental low-frequency phonon modes. Then, we have ... [more ▼]

Raman and infrared spectra of urea single crystals have been calculated using the density functional theory. This allowed us to assign the remaining experimental low-frequency phonon modes. Then, we have determined the sign of the second-harmonic nonlinear optical susceptibility coefficient in urea to be negative, clarifying a long debate in the literature. Finally, we computed for the first time the electro-optic coefficients of urea. We found that the electronic and ionic contributions have a similar order of magnitude and an opposite sign, yielding a smaller value than that expected, and necessitating further experimental clarifications. [less ▲]

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See detailZwitterionic i-motif structures are preserved in DNA negatively charged ions produced by electrospray mass spectrometry
Rosu, Frédéric ULiege; Gabelica, Valérie ULiege; Joly, Laure ULiege et al

in Physical Chemistry Chemical Physics [=PCCP] (2010), 12

DNA cytosine-rich strands can fold into an intercalated motif (i-motif) structure. The i-motif is formed by mutually intercalated duplexes containing proton-mediated C-H(+)-C (cytosine-proton-cytosine ... [more ▼]

DNA cytosine-rich strands can fold into an intercalated motif (i-motif) structure. The i-motif is formed by mutually intercalated duplexes containing proton-mediated C-H(+)-C (cytosine-proton-cytosine) base pairs. Negatively charged ions of DNA i-motifs produced by electrospray mass spectrometry are therefore zwitterionic if the base pairing motif is preserved in the gas phase. Here we used IRMPD spectroscopy and ion mobility spectrometry to assess whether i-motif structures were preserved in the gas phase. We first investigated the IRMPD spectral signature of the tetramer [dC(6)](4), which can only be formed via C-H(+)-C base pairing, compared to the single strand dC(6). The IR signature of i-motif formation is an apparent broadening of the band at 1650 cm(-1). DFT calculations show this apparent broadening is actually due to blue-shifts of the NH(2) scissoring modes and red shifts of C[double bond, length as m-dash]O stretching modes. We then investigated the gas-phase conformations of the telomeric sequence d(CCCAAT)(3)CCC, that can form an intramolecular i-motif, by performing IRMPD spectroscopy and ion mobility spectrometry as a function of the charge state. We show that the negative ions of the lowest charge states correspond to a preserved i-motif structure. This is the first demonstration of the native extraction of solution-phase zwitterionic nucleic acids using negative electrospray ionization. [less ▲]

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See detailThe role of the support in COads monolayer electrooxidation on Pt nanoparticles : Pt/WOx vs. Pt/C.
Micoud, Fabrice; Maillard, Frédéric; Bonnefont, Antoine et al

in Physical Chemistry Chemical Physics [=PCCP] (2010), 12

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