Search

The well-established and rapidly expanding field of molecular processes in excited systems, facilitated by the use of light sources, garners significant research interest from numerous experimental and theoretical groups worldwide. This highly interdisciplinary field establishes extensive connections with atomic, molecular and optical physics, astrophysics, biophysics, physical chemistry, solid-state physics and even molecular biology. The present topic provides an advanced overview of research activities in cutting-edge areas such as ultrafast lasers, nanoscale systems, atomic and molecule collisions on surfaces and molecular photofragmentation processes. The contributions to this subject encompass experimental, theoretical and computational studies conducted both at the fundamental level, exploring elementary mechanisms, and at a more applied level, addressing the requirements of diverse applications in nanotechnology and materials science. [ABSTRACT FROM AUTHOR]

Differential and total reaction cross sections for the Cs+ICH3→CsI+CH3 system have been measured as a function of the collision energy by using the crossed beam technique. The analysis of the center-of-mass angular and recoil velocity distribution of the products indicated: (a) a backward peak character corresponding to a direct rebound mechanism at low collision energy; (b) over the collision energy range from 0.15 up to 0.56 eV, the backward character shifts to near sideways scattering. A direct interaction with product repulsion (DIPR) model analysis of this collision energy evolution showed an increasing participation of bent transition state configurations, which might be in competition with the purely collinear one at lower collision energy; (c) that the average products’ translational energy E’T increases approximately linearly with increasing collision energy ET as follows: E’T/kJ mol-1 =0.62 ET/kJ mol-1+58.5. Complete laboratory differential reaction cross-section measurements were carried out at 21 different relative velocities, then integrated and normalized to yield the total flux and reaction cross section in relative units. Over the available range of ET, σR(ET) shows a minimum at ET[bar_over_tilde:_approx._equal_to]0.23 eV. A comparison of the present excitation function shape with current theoretical treatments is also reported. [ABSTRACT FROM AUTHOR]

The elongation of metallic nanoparticles (NPs) embedded in a dielectric matrix after irradiation with swift heavy ions is a phenomenon that has been known for several years. However, the precise mechanism behind this deformation process is still not fully understood, primarily due to the dearth of information during intermediate stages of deformation. In this study, we report the continuation of our previous work [Peña-Rodríguez et al., Sci. Rep. 7(1), 922 (2017)], exploiting the strong dependence of the localized surface plasmon resonance on the aspect ratio of elongated metal NPs to study the elongation kinetics in situ. In situ optical absorption spectra were measured using a polarizing beam splitter to separate the longitudinal and transverse plasmon modes of the anisotropic NPs. Then, the detailed geometrical and compositional parameters were determined from a fit of these spectra. The use of linearly polarized light allowed for a more accurate analysis of the elongation kinetics, particularly useful in the first stages, where longitudinal and transverse modes overlap. [ABSTRACT FROM AUTHOR]

Quasi-classical trajectory (QCT) calculations have been carried out on a new implementation of the first singlet state a˜1A′ potential energy surface (PES) of the C(1D)+H2 system based on a set of 1748 ab initio points previously reported. The implementation is performed by using the Reproducing Kernel Hilbert Space (RKHS) interpolation method, which allows the fast evaluation of the PES values and, particularly, their gradients analytically. Although there is a general good correspondence between the present surface and the previous version, the new PES is free of spurious small scale features and permits a faster evaluation of the PES and its gradients. The QCT results on the present PES are in general good agreement with those obtain on the previous PES. [Copyright &y& Elsevier]

Multiphoton 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(2E3/2) Rydberg state with different degrees of vibrational excitation, revealing an energy compensation effect as the R-chain complexity increases. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics leading to the C–N bond cleavage in methylamine (CH3NH2) are investigated upon photoexcitation in the blue edge of the first absorption A-band, in the 198–204 nm range. Velocity map images of the generated methyl (CH3) fragment detected in specific vibrational modes, i.e., ν = 0, ν1 = 1, and ν2 = 1, through resonance enhanced multiphoton ionization, are presented along with the corresponding translational energy distributions and the angular analysis. The experimental results are complemented by high-level ab initio calculations of potential energy curves as a function of the C–N bond distance. While a similar single Boltzmann-type contribution is observed in all the translational energy distributions measured, the speed-dependent anisotropy parameter obtained through the angular analysis reveals the presence of two different mechanisms. Prompt dissociation through the conical intersection between the A ̃ 1 A ′ first excited state and the ground state located in the exit channel is, indeed, revealed as a minor channel. In contrast, slow dissociation on the ground state, presumably from frustrated N–H bond cleavage trajectories, constitutes the major reaction pathway leading to the methyl formation. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of methylamine (CH3NH2) upon excitation in the blue edge of the first absorption A-band, in the 198–203 nm range, are investigated by means of nanosecond pump–probe laser pulses and velocity map imaging combined with H(2S)-atom detection through resonance enhanced multiphoton ionization. The images and corresponding translational energy distributions for the H-atoms produced show three different contributions associated with three reaction pathways. The experimental results are complemented by high-level ab initio calculations. The potential energy curves computed as a function of the N–H and C–H bond distances allow us to draw a picture of the different mechanisms. Major dissociation occurs through N–H bond cleavage and it is triggered by an initial geometrical change, i.e., from a pyramidal configuration of the C–NH2 with respect to the N atom to a planar geometry. The molecule is then driven into a conical intersection (CI) seam where three outcomes can take place: first, threshold dissociation into the second dissociation limit, associated with the formation of CH3NH ( A ̃) , is observed; second, direct dissociation after passage through the CI leading to the formation of ground state products; and third, internal conversion into the ground state well in advance to dissociation. While the two last pathways were previously reported at a variety of wavelengths in the 203–240 nm range, the former had not been observed before to the best of our knowledge. The role of the CI and the presence of an exit barrier in the excited state, which modify the dynamics leading the two last mechanisms, are discussed considering the different excitation energies used. [ABSTRACT FROM AUTHOR]

In this work, laser‐induced periodic surface structures (LIPSS) are generated on the surface of thin films of poly(trimethylene terephthalate) (PTT) fabricated by spin coating on silicon. Previous studies have shown the appearance of LIPSS in this type of materials with femtosecond laser pulses in the near‐infrared region of the spectrum, despite the extremely low absorption of the polymer. The present work consists of an exploration of the effect of adding complexity to the femtosecond laser fields employed for irradiation. Changes in the repetition rate of the pulse train, the pulse duration, and the pulse temporal chirp are explored, and conditions for optimum LIPSS formation are identified. The effects of these modifications on the polymer surface topography, assessed by atomic force microscopy, are described and discussed. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of alkyl iodides along the C–I bond are captured by attosecond extreme-ultraviolet (XUV) transient absorption spectroscopy employing resonant ∼20 fs UV pump pulses. The methodology of previous experiments on CH3I [Chang et al., J. Chem. Phys. 154, 234301 (2021)] is extended to the investigation of a C–I bond-breaking reaction in the dissociative A-band of C2H5I, i-C3H7I, and t-C4H9I. Probing iodine 4d core-to-valence transitions in the XUV enables one to map wave packet bifurcation at a conical intersection in the A-band as well as coherent vibrations in the ground state of the parent molecules. Analysis of spectroscopic bifurcation signatures yields conical intersection crossing times of 15 ± 4 fs for CH3I, 14 ± 5 fs for C2H5I, and 24 ± 4 fs for i-C3H7I and t-C4H9I, respectively. Observations of coherent vibrations, resulting from a projection of A-band structural dynamics onto the ground state by resonant impulsive stimulated Raman scattering, indirectly reveal multimode C–I stretch and CCI bend vibrations in the A-bands of C2H5I, i-C3H7I, and t-C4H9I. [ABSTRACT FROM AUTHOR]

The article reports on real-time femtosecond observation of the primary bond-twisting dynamics of trans- and cis-stilbene anion radicals made by electron attachment in a molecular beam. The result highlights that the significance of studying the anion dynamics in the isolated molecule revealing the actual time scales in primary dynamics involved and the coherent vibration motion involved. It concludes that the observed behavior for twisting is different from that reported in the solution phase.

[Display omitted] • Theoretical and experimental research on Ce and Er co-doped hydroxyapatite has been conducted. • The formation of the HAp structure was confirmed by Raman and FTIR spectra for all the samples. • Density increased from 3.1745 to 3.1950 g cm−3 with adding of Ce. • The photon energy rises once the linear absorption coefficients decrease. In this work, we have investigated Ce3+ and Er3+ co-doped hydroxyapatite (HAp) structures both theoretically and experimentally for the first time. The Ce3+ content was incrementally varied in steps of 0.13 at. %, ranging from 0.13 at. % to 0.78 at. %. Meanwhile, the Er3+ content remained constant at 0.39 at. % for all samples. We employed X-ray diffraction, Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis, differential scanning calorimetry, and in vitro biocompatibility tests to examine the prepared samples. Our findings demonstrate that the thermal behavior, morphology, and other crystal structure-related parameters are significantly influenced by the concentration of Ce3+. The formation of HAp structures was confirmed through FTIR and Raman spectroscopic analyses. Furthermore, we conducted theoretical calculations to determine the linear absorption coefficient, density of states, and bandgap. These calculations revealed that the addition of Ce3+ atoms at varying concentrations resulted in an increase in density from 3.174 to 3.195 g cm−3, while the bandgap gradually decreased from 4.16 to 4.10 eV, except for the 0.26Ce-0.39Er-HAp and 0.52Ce-0.39Er-HAp compositions, where the energy bandgap exhibited an increase. [ABSTRACT FROM AUTHOR]

The 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. [ABSTRACT FROM AUTHOR]

Clocking 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. [ABSTRACT FROM AUTHOR]

Directed assembly of gold nanorods through the use of dithiolated molecular linkers is one of the most efficient methodologies for the morphologically controlled tip-to-tip assembly of this type of anisotropic nanocrystals. However, in a direct analogy to molecular polymerization synthesis, this process is characterized by difficulties in chain-growth control over nanoparticle oligomers. In particular, it is nearly impossible to favor the formation of one type of oligomer, making the methodology hard to use for actual applications in nanoplasmonics. We propose here a light-controlled synthetic procedure that allows obtaining selected plasmonic oligomers in high yield and with reaction times in the scale of minutes by irradiation with low fluence near-infrared (NIR) femtosecond laser pulses. Selective inhibition of the formation of gold nanorod n-mers (trimers) with a longitudinal localized surface plasmon in resonance with a 800 nm Ti:sapphire laser, allowed efficient trapping of the (n - 1)-mers (dimers) by hot spot mediated photothermal decomposition of the interparticle molecular linkers. Laser irradiation at higher energies produced near-field enhancement at the interparticle gaps, which is large enough to melt gold nanorod tips, offering a new pathway toward tip-to-tip welding of gold nanorod oligomers with a plasmonic response at the NIR. Thorough optical and electron microscopy characterization indicates that plasmonic oligomers can be selectively trapped and welded, which has been analyzed in terms of a model that predicts with reasonable accuracy the relative concentrations of the main plasmonic species. [ABSTRACT FROM AUTHOR]

Conjugated polymer blends coupled by Förster resonance energy transfer (FRET) have been widely exploited to achieve optically pumped lasers operating at very low pumping thresholds. Among the plaid of conjugated polymers and molecules exploited for optical gain, fluorene‐based polymers are considered front‐runners, based on their high photoluminescence quantum yields, large optical gain coefficients, and their processability assets in films of high optical quality. Two archetypes of polymers with these properties are poly(9,9‐dioctyl‐fluorene) and its green‐emitting relative poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) that work as excellent FRET‐coupled blends but unexpectedly do not exhibit stimulated emission. In this study, light is shed upon the optical gain limiting factors of these blends. Upon investigating a series of poly(diarylfluorene‐co‐N‐phenyl) polymers bearing a different number of phenyl units inserted between the fluorenes (NPhs, N = 1, 2, 3), important improvements are revealed in the photoluminescence quantum yields and stimulated emission properties, as well as harnessing of exciton‐exciton annihilation. These effects are ascribed to disruption of exciton transport in NPhs motivated by changes in chain conformation and molecular packing upon phenyl‐insertion. [ABSTRACT FROM AUTHOR]

A pulse shaping control experiment on multiphoton ionization of the methyl iodide (CH3I) molecule is reported. A range of phase masks were applied in the Fourier plane of a 4fpulse shaper containing a spatial light modulator, causing spectro-temporal modulation in the 540 nm pulses synthesized in an optical parametric amplifier. The ionization process was studied through velocity map imaging of outgoing photoelectrons. Four main ionization channels were identified, with relative yields that are dependent on the pulse shape applied, indicating that the ionization routes can be steered through light manipulation to some extent. The main mechanism for control seems to derive from peak intensity effects, but some features observed in the photoelectron spectra defy this explanation. The role of resonances at the three-photon level is discussed. [ABSTRACT FROM AUTHOR]

The C–C bond dissociation channel of the ethyl (CH 3 –CH 2 ) radical is investigated at 197.4, 199.98 and 201 nm by velocity map imaging and resonance enhanced multiphoton ionisation (REMPI) detection of the produced CH 3 fragments. On the light of high-level abinitio calculations performed in this work, up to four dissociation pathways are identified leading, respectively, to ground state CH 3 radicals in correlation with CH 2 fragments in the first four electronic states. The major pathway is associated with threshold dissociation over an exit barrier located at the point of a conical intersection between the initially populated 3 p A ′ state and a dissociative valence state. As discussed in the text, the concomitance of both features opens the narrow window in which C–C bond dissociation occurs for ethyl and, presumably, for other similar alkyl radicals. [ABSTRACT FROM AUTHOR]

Bimetallic nanoparticles display unique physical and chemical properties, including improved chemical stability, enhanced optical properties, or higher catalytic activity. Here, a synthetic methodology is described to obtain bimetallic heterostructures and alloyed plasmonic nanocrystals through the irradiation of colloidal Au@Ag core–shell nanorods (Au@Ag NRs) with femtosecond laser pulses. Depending on the energy deposited on the Au@Ag NRs, different morphologies and degrees of alloying are obtained, such as hot‐dog‐like and rice‐like (partially alloyed) NRs, as well as fully alloyed nanospheres. By using advanced electron microscopy techniques and energy‐dispersive X‐ray spectroscopy (EDX) tomography, both the morphology and the elemental distribution of the irradiated nanoparticles can be disclosed, and correlated to detailed investigations of their optical properties using electromagnetic simulations. The wide variety of bimetallic species provided by the proposed approach is a clear indication of the potential of combining synthetic colloidal methods with fs‐pulsed laser irradiation for the fabrication of unique multielemental nanoparticles. The resulting control over size and composition raises promising prospects for catalytic, plasmonic, and magnetic applications of multimetallic nanocrystals. [ABSTRACT FROM AUTHOR]

Upconversion 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. [ABSTRACT FROM AUTHOR]

The correlation between chemical structure and predissociation dynamics has been evaluated for a series of linear and branched alkyl iodides with increasing structural complexity by means of femtosecond time-resolved velocity map imaging experiments following excitation on the second absorption band (B-band) at around 201 nm. The time-resolved images for the iodine fragment are reported and analyzed in order to extract electronic predissociation lifetimes and the temporal evolution of the anisotropy while the experimental results are supported by ab initio calculations of the potential energy curves as a function of the C-I distance. Remarkable similarities are observed for all molecules consistent with a major predissociation of the initially populated bound Rydberg states 6A″ and 7A′ through a crossing with the purely repulsive states 7A″, 8A′ and 8A″ leading to a major R + I*(2P1/2) (R = CH3, C2H5, n-C3H7, n-C4H9, i-C3H7 and t-C4H9) dissociation channel. The reported electronic predissociation lifetimes are found to decrease for an increasing size of the linear radical, reflecting the shifts observed in the position of the crossings in the potential energy curves, and very likely a greater non-adiabatic coupling between the initially populated Rydberg states and the repulsive states leading to dissociation induced by other coordinates associated to key vibrational normal modes. The loss of anisotropy is fully accounted for by the parent molecular rotation during predissociation and the rotational temperature of the parent molecule in the molecular beam is reasonably derived. [ABSTRACT FROM AUTHOR]

The first calculations of state-to-state reaction probabilities and product state-resolved integral cross sections at selected collision energies (0.05, 0.1, 0.5, and 1.0 eV) for the title reaction on the ab initio potential energy surface of [Zanchet et al. J. Phys. Chem. A 110, 12017 (2006)] with the OH reagent in selected rovibrational states (v=0–2, j=0–5) have been carried out by means of the real wave packet (RWP) and quasiclassical trajectory (QCT) methods. State-selected total reaction probabilities have been calculated for total angular momentum J=0 in a broad range of collision energies. Integral cross sections and state-specific rate coefficients have been obtained from the corresponding J=0 RWP reaction probabilities for initially selected rovibrational states by means of a capture model. The calculated RWP and QCT state-selected rate coefficients are practically temperature independent. Both RWP and QCT reaction probabilities, integral cross sections, and rate coefficients are almost independent of the initial rotational excitation. The RWP results are found to be in an overall good agreement with the corresponding QCT results. The present results have been compared with earlier wave packet calculations carried out on the same potential energy surface. [ABSTRACT FROM AUTHOR]

The real time photodissociation dynamics of CH3I from the A band has been studied experimentally and theoretically. Femtosecond pump-probe experiments in combination with velocity map imaging have been carried out to measure the reaction times (clocking) of the different (nonadiabatic) channels of this photodissociation reaction yielding ground and spin-orbit excited states of the I fragment and vibrationless and vibrationally excited (symmetric stretch and umbrella modes) CH3 fragments. The measured reaction times have been rationalized by means of a wave packet calculation on the available ab initio potential energy surfaces for the system using a reduced dimensionality model. A 40 fs delay time has been found experimentally between the channels yielding vibrationless CH3(ν=0) and I(2P3/2) and I*(2P1/2) that is well reproduced by the calculations. However, the observed reduction in delay time between the I and I* channels when the CH3 fragment appears with one or two quanta of vibrational excitation in the umbrella mode is not well accounted for by the theoretical model. [ABSTRACT FROM AUTHOR]

The H++D2(v=0,j=0)→HD+D+ reaction has been theoretically investigated by means of a time independent exact quantum mechanical approach, a quantum wave packet calculation within an adiabatic centrifugal sudden approximation, a statistical quantum model, and a quasiclassical trajectory calculation. Besides reaction probabilities as a function of collision energy at different values of the total angular momentum, J, special emphasis has been made at two specific collision energies, 0.1 and 0.524 eV. The occurrence of distinctive dynamical behavior at these two energies is analyzed in some detail. An extensive comparison with previous experimental measurements on the Rydberg H atom with D2 molecules has been carried out at the higher collision energy. In particular, the present theoretical results have been employed to perform simulations of the experimental kinetic energy spectra. [ABSTRACT FROM AUTHOR]

The H++H2 exchange reaction has been studied theoretically by means of a different variety of methods as an exact time independent quantum mechanical, approximate quantum wave packet, statistical quantum, and quasiclassical trajectory approaches. Total and state-to-state reaction probabilities in terms of the collision energy for different values of the total angular momentum obtained with these methods are compared. The dynamics of the reaction is extensively studied at the collision energy of Ecoll=0.44 eV. Integral and differential cross sections and opacity functions at this collision energy have been calculated. In particular, the fairly good description of the exact quantum results provided by the statistical quantum method suggests that the dynamics of the process is governed by an insertion mechanism with the formation of a long-lived collision complex. [ABSTRACT FROM AUTHOR]

In this paper we report a combined experimental and theoretical study on the dynamics of the insertion reaction C(1D)+D2 at 15.5 kJ mol-1 collision energy. Product angular and velocity distributions have been obtained in crossed beam experiments and quasiclassical trajectory (QCT) and rigorous statistical calculations have been performed on the recent and accurate ab initio potential energy surface of Bussery-Honvault, Honvault, and Launay at the energy of the experiment. The molecular-beam results have been simulated using the theoretical calculations. Good agreement between experiment and both QCT and statistical predictions is found. [ABSTRACT FROM AUTHOR]

An experimental and theoretical investigation of the collision energy dependence of the HD(ν[sup ′]=2,j[sup ′]) rotational product state distribution for the H+D[sub 2] reaction in the collision energy range of E[sub col]=1.30–1.89 eV has been carried out. Theoretical results based on time-dependent and time-independent quantum mechanical methods agree nearly perfectly with each other, and the agreement with the experiment is good at low collision energies and very good at high collision energies. This behavior is in marked contrast to a previous report on the HD(ν[sup ′]=3,j[sup ′]) product state rotational distribution [Pomerantz et al., J. Chem. Phys. 120, 3244 (2004)] where a systematic difference between experiment and theory was observed, especially at the highest collision energies. The reason for this different behavior is not yet understood. In addition, this study employs Doppler-free spectroscopy to resolve an ambiguity in the E, F–X resonantly enhanced multiphoton ionization transition originating from the HD(ν[sup ′]=2,j[sup ′]=1) state, which is found to be caused by an accidental blending with the transition coming from the HD(ν[sup ′]=1,j[sup ′]=14) state. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present experimental rotational distributions for the reaction H+D[sub 2]→HD(ν[sup ′]=3,j[sup ′])+D at eight different collision energies between 1.49 and 1.85 eV. We combine a previous measurement of the state-resolved excitation function for this reaction [Ayers et al., J. Chem. Phys. 119, 4662 (2003)] with the current data to produce a map of the relative reactive cross section as a function of both collision energy and rotational quantum number (an E–j[sup ′] plot). To compare with the experimental data, we also present E–j[sup ′] plots resulting from both time-dependent and time-independent quantum mechanical calculations carried out on the BKMP2 surface. The two calculations agree well with each other, but they produce rotational distributions significantly colder than the experiment, with the difference being more pronounced at higher collision energies. Disagreement between theory and experiment might be regarded as surprising considering the simplicity of this system; potential causes of this discrepancy are discussed. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A new implementation is presented for the potential energy surface (PES) of the 1 [SUP2]A" state of the N([SUP2]D)+ H[SUB2] system based on a set of 2715 ab initio points resulting from the multireference configuration interaction (MRCI) calculations. The implementation is carried out using the reproducing Kernel Hilbert Space interpolation method. Range parameters, via bond-order-like coordinates, are properly chosen to render a sufficiently short-range three-body interaction and a regularization procedure is invoked to yield a globally smooth PES. A fast algorithm, with the help of low-order spline reproducing kernels, is implemented for the computation of the PES and, particularly, its gradients, whose fast evaluation is essential for large scale quasi-classical trajectory calculations. It is found that the new PES can be evaluated more than ten times faster than that of an existing (old) PES based on a smaller number (1141) of data points resulting from the same MRCI calculations and a similar interpolation procedure. Although there is a general good correspondence between the two surfaces, the new PES is in much better agreement with the ab initio calculations, especially in key stationary point regions including the C[SUB2ν] (minimum, the C[SUB2ν] transition state, and the N-H-H linear barrier. Moreover, the new PES is free of spurious small scale features. Analytic gradients are made available in the new PES code to further facilitate quasiclassical trajectory calculations, which have been performed and compared with the results based on the old surface. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Aimed at filling the gap in the theoretical studies of the CH 3 's photo-dissociation. • Our results look promising reproducing the same trend as state of the art experiments. • The method used allows the interpretation of the internal mechanisms of the process. Abstract The photodissociation dynamics of methyl radical from selected vibrational levels of the 3 s and 3 p z Rydberg states has been studied using the trajectory surface hopping method on one-dimensional potential energy curves along the carbon-hydrogen dissociative coordinate and the non-adiabatic couplings between them, calculated by ab initio methods. Lifetimes and product distributions have been obtained for all the studied vibrational levels and compared with previous theoretical and experimental works. The theoretical lifetimes tend to decrease as vibrational excitation increases in accordance with experimental results. The agreement, however, is only qualitative considering the reduced dimensionality of the model. [ABSTRACT FROM AUTHOR]

Abstract ZnO powder has been synthesized, characterized experimentally and its theoretical modeling carried out by density functional theory (DFT). The experimental and theoretical results were compared with each other and with the available data in the literature. A detailed crystal structure analysis was carried out using X-ray diffraction (XRD) data. Experimental and theoretical FTIR analysis, energy gap and density of states and electronic band structure calculations have been done for a complete characterization of the material. The surface morphology has been investigated by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. It has been found that the electron excitation of ZnO can occur most probably at the Γ-Γ point, where the energy gap has the lowest value between the valance and conduction bands. [ABSTRACT FROM AUTHOR]

The irradiation of gold nanorod colloids with a femtosecond laser can be tuned to induce controlled nanorod reshaping, yielding colloids with exceptionally narrow localized surface plasmon resonance bands. The process relies on a regime characterized by a gentle multishot reduction of the aspect ratio, whereas the rod shape and volume are barely affected. Successful reshaping can only occur within a narrow window of the heat dissipation rate: Low cooling rates lead to drastic morphological changes, and fast cooling has nearly no effect. Hence, a delicate balance must be achieved between irradiation fluence and surface density of the surfactant on the nanorods. This perfection process is appealing because it provides a simple, fast, reproducible, and scalable route toward gold nanorods with an optical response of exceptional quality, near the theoretical limit. [ABSTRACT FROM AUTHOR]

Chemical reaction dynamics and, particularly, photodissociation in the gas phase are generally studied using pump-probe schemes where a first laser pulse induces the process under study and a second one detects the produced fragments. Providing an efficient detection of ro-vibrationally state-selected photofragments, the resonance enhanced multiphoton ionization (REMPI) technique is, without question, the most popular approach used for the probe step, while non-resonant multiphoton ionization (NRMPI) detection of the products is scarce. The main goal of this work is to test the sensitivity of the NRMPI technique to fragment vibrational distributions arising from molecular photodissociation processes. We revisit the well-known process of methyl iodide photodissociation in the A-band at around 280 nm, using the velocity-map imaging technique in conjunction with NRMPI of the methyl fragment. The detection wavelength, carefully selected to avoid any REMPI transition, was scanned between 325 and 335nm seeking correlations between the different observables--the product vibrational, translational and angular distributions--and the excitation wavelength of the probe laser pulse. The experimental results have been discussed on the base of quantum dynamics calculations of photofragment vibrational populations carried out on available ab initio potential-energy surfaces using a four-dimensional model. [ABSTRACT FROM AUTHOR]

Boosting the Stimulated Emission Properties of Host:Guest Polymer Blends by Inserting Chain Twists in the Host Polymer (Adv. Funct. Keywords: amplified spontaneous emissions; dihedral angles; excited-state dynamics; optical gain; polymer chains; pump-probes EN amplified spontaneous emissions dihedral angles excited-state dynamics optical gain polymer chains pump-probes 1 1 1 11/29/22 20221124 NES 221124 B Amplified Spontaneous Emission b In article number 2206723, Juan Cabanillas-González, Johannes Gierschner, Jinyi Lin and co-workers report on how the spontaneous and stimulated emission properties of conjugated polymer blends are promoted through exciton transport disruption. Amplified spontaneous emissions, dihedral angles, excited-state dynamics, optical gain, polymer chains, pump-probes. [Extracted from the article]

Abstract: N-butylpyridinium chloride ([bpy][Cl]) is an ionic liquid (IL) extensively employed as an effective catalyst for many chemical reactions. Therefore, precise monitoring of its concentration can ensure the desired high yields in these catalyzed chemical processes. In this work, a fluorescence study has been carried out to determine the concentration of [bpy][Cl] in aqueous solution. A light emitting diode (LED), a continuous wave laser diode (CWLD), and a femtosecond pulsed laser (FPL) have been employed as light sources to electronically excite IL samples at a central wavelength of 400nm. The measured fluorescence spectra obtained at different concentrations have been used to design three mathematical models for each one of the light sources. These models rely on artificial neural networks (ANNs) to assess the concentration of IL aqueous solutions in a wide range of concentrations. ANNs have been selected thanks to their ability to discover and adequately interpret nonlinear relationships among datasets. ANNs have been successful due to the existence of a nonlinear dependence between the IL fluorescence signal and its concentration, most likely due to the inner filter effect. The three light sources employed were suitable to fulfill the goal (mean prediction errors were 4.9%, 2.5%, and 1.7% for the LED, CWLD, and FPL models, respectively). These results suggest the existence of a potential source of reliable sensors based on the combination of fluorescence and ANNs. Furthermore, the accurate concentration estimation of many fluorescent compounds in aqueous solution appears achievable and, therefore, applicable to multiple chemical processes. [Copyright &y& Elsevier]

Abstract: Kelvin probe force microscopy images show that the surface potential of graphite changes with time as the contamination covers its surface. Using mass spectrometry we identify the molecular mass of the contaminants to be compatible with that of tetracene, a polycyclic aromatic hydrocarbon (PAH), and its isomers. A combination of desorption and Kelvin probe force microscopy experiments plus theoretical calculations confirms that these molecules are the main contaminant for graphitic surfaces in air ambient conditions. Interestingly, when the sample temperature is increased above ∼50°C the molecules are desorbed and the surface potential becomes fairly homogeneous, suggesting that graphitic surfaces should be almost atomically clean above this temperature. PAHs are potent atmospheric pollutants, potentially carcinogenic, that consist of fused aromatic rings. Incomplete combustion of organic materials can increase the concentration of PAHs in the atmosphere, which in urban regions is enough to totally cover the surface of graphite in a time period that varies from minutes to a few hours. One of the consequences of the adsorption of molecules on graphene is the doping of its surface and the variation of the charge neutrality point originated by the charge transfer between graphene and the contamination layer. [Copyright &y& Elsevier]

The formation of cationic clusters in the laser ablation of CdS targets has been investigated as a function of wavelength and fluence by mass spectrometric analysis of the plume. Ablation was carried out at the laser wavelengths of 1064, 532, 355, and 266 nm in order to scan the interaction regimes below and above the energy band gap of the material. In all cases, the mass spectra showed stoichiometric Cd nS and nonstoichiometric Cd nS, Cd nS, and Cd nS clusters up to 4900 amu. Cluster size distributions were well represented by a log-normal function, although larger relative abundance for clusters with n=13, 16, 19, 34 was observed (magic numbers). The laser threshold fluence for cluster observation was strongly dependent on wavelength, ranging from around 16 mJ/cm2 at 266 nm to more than 300 mJ/cm2 at 532 and 1064 nm. According to the behavior of the detected species as a function of fluence, two distinct families were identified: the “light” family containing S and Cd+ and the “heavy” clusterized family grouping Cd and Cd nS. In terms of fluence, it has been determined that the best ratio for clusterization is achieved close to the threshold of appearance of clusters at all wavelengths. At 1064, 532, and 355 nm, the production of “heavy” cations as a function of fluence showed a maximum, indicating the participation of competitive effects, whereas saturation is observed at 266 nm. In terms of relative production, the contribution of the “heavy” family to the total cation signal was significantly lower for 266 nm than for the longer wavelengths. Irradiation at 355 nm in the fluence region of 200 mJ/cm2 has been identified as the optimum for the generation of large clusters in CdS. [ABSTRACT FROM AUTHOR]

Abstract: Nanostructured deposits of TiO2 were grown on Si (100) substrates by laser ablating a TiO2 sintered target in vacuum or in oxygen using a Ti:sapphire laser delivering 80fs pulses. The effect of the laser irradiation wavelength on the obtained nanostructures, was investigated using 800, 400 and 266nm at different substrate temperatures and pressures of oxygen. The composition of the deposits was characterized using X-ray photoelectron spectroscopy (XPS) and the surface morphology was studied by environmental scanning electron microscopy (ESEM) and atomic force microscopy (AFM). Deposits are absent of microscopic droplets in all conditions explored. The best deposits, constituted by nanoparticles of an average diameter of 30nm with a narrow size distribution, were obtained at the shorter laser wavelength of 266nm under vacuum at substrate room temperature. [Copyright &y& Elsevier]

Matrix-assisted laser desorption ionization (MALDI) was applied to determine the relative efficiencies for attachment of alkali cations to poly(ethylene glycol) polymers. The solvent-free sample preparation method was employed in order to discriminate the gas-phase polymer-cation complex formation mechanism from solubility and co-crystallization effects. We show that the cohesion energy of the cation precursor has a strong influence on the outcome of the MALDI measurements. This potential drawback is circumvented by the simultaneous use of alkali salts of similar lattice energy. The experiments include chain polymers of different length (PEG600 and PEG1000) and alkali cations of different size (Na+, K+, Cs+). We found that the attachment efficiencies decrease with growing cation size. This decrease is significantly more rapid for the shorter PEG600 polymers. These results corroborate the general trends observed in earlier studies, but correct the dependence on alkali cation size assessed in previous MALDI experiments with the conventional dried-droplet sample preparation method. [ABSTRACT FROM AUTHOR]

RRKM calculations and MP2/6-31G(d,p) quasiclassical trajectories (QCT) were performed to investigate the H2 elimination in the photodissociation of vinyl chloride at 193 nm. The kinetic study involved nine elementary steps and the QCT investigation was made for the relevant reaction channels. The trajectories were initiated at the transition states using a microcanonical, quasiclassical normal-mode sampling. Comparison between the calculated product energy distributions and the available experimental data is discussed. Overall, the present results (RRKM and QCT) suggest that the direct three-center elimination, which may occur via two similar transition states, is the dominant mechanism for H2 production. [Copyright &y& Elsevier]

The technique of resonance-enhanced multiphoton ionization with time-of-flight mass spectrometry (REMPI-TOF MS) has been used to study the photodissociation of fully deuterated dimethyl sulfide (CD3SCD3) following excitation at several wavelengths within the first absorption band (215−229 nm). Analysis of measured time-of-flight profiles of the nascent CD3 products indicates a strongly anisotropic photodissociation, with approximately 70−80% of the available energy appearing as fragment recoil translation. A hybrid statistical−impulsive dissociation model predicts a photolysis wavelength dependence of the translational energy release that compares favorably with experiment, supporting the suggestion (Manaa, M. R.; Yarkony, D. R. J.Am.Chem.Soc. 1994, 116, 11444) that both the 1A' ' and 21A' ' excited states play an important role in the photodissociation process. An analysis of nascent CD3 (μ, v, J) vector correlations, where the fragments are assumed to recoil axially along the CD3S−CD3 bond, adequately accounts for the observed probe laser polarization dependence of velocity-selected REMPI spectra. The weak observed rotational excitation of the methyl fragments originates from zero-point vibrational motion of the dissociating parent molecule. [ABSTRACT FROM AUTHOR]

Nanostructured thin films of Co-doped zinc sulfide were synthesized through femtosecond pulsed laser deposition. The scheme involved ablation of physically mixed Co and ZnS with pairs of ultrashort pulses separated in time in the 0–300 ps range. In situ monitorization of the deposition process was carried out through a simultaneous reflectivity measurement. The crystallinity of generated nanoparticles and the inclusion of Co in the ZnS lattice is demonstrated by transmission electron microscopy and energy dispersive X-ray microanalysis (TEM-EDX) characterization. Surface morphology, Raman response, and photoluminescence of the films have also been assessed. The role of interpulse temporal separation is most visible in the thickness of the films obtained at the same total fluence, with much thicker films deposited with short delays than with individual uncoupled pulses. The proportion of Co in the synthesized doped ZnS nanoparticles is found to be substantially lower than the original proportion, and practically independent on interpulse delay. [ABSTRACT FROM AUTHOR]

One of the most important and distinctive features of plasmonic nanostructures is their ability to confine large electromagnetic fields on nanometric volumes; i.e., the so-called hot spots. The generation, control and characterization of the hot spots are fundamental for several applications, like surface-enhanced spectroscopies. In this work, we characterize the near-field distribution and enhancement of nanostructured gold thin films fabricated by glancing angle deposition magnetron sputtering. These films are composed of columnar nanostructures with high roughness and high density of inter-columnar gaps, where the electromagnetic radiation can be confined, generating hot spots. As expected, the hot spots are localized in the gaps between adjacent nanocolumns and we use scattering-type scanning near-field optical microscopy to image their distribution over the surface of the samples. The experimental results are compared with finite-difference time-domain simulations, finding an excellent agreement between them. The spectral dependence of the field-enhancement is also studied with the simulations, together with surface-enhanced Raman spectroscopy at different excitation wavelengths in the visible-NIR range, proving a broad-band response of the substrates. These findings may result in interesting applications in the field of surface-enhanced optical spectroscopies or sensing. [ABSTRACT FROM AUTHOR]