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This is the first comprehensive investigation on the anionic species formed during collisions of fast neutral potassium (K) atoms with neutral hexachlorobenzene (C6Cl6) molecules in the laboratory frame range from 10 up to 100 eV. In such ion-pair formation experiments we also report a novel K+ energy loss spectrum obtained in the forward scattering giving evidence of the most accessible electronic states. The vertical electron affinity of (−3.76 ± 0.20) eV has been obtained and assigned to a purely repulsive transition from the C6Cl6 ground state to a state of the temporary negative ion yielding Cl− formation. These experimental findings are also supported by state-of-the art theoretical calculations on the electronic structure of C6Cl6 in the presence of a potassium atom and are used for analysing the lowest unoccupied molecular orbitals participating in the collision process. From the time-of-flight mass spectra recorded in the wide collision energy range, more than 80% of the total anion yield is due to the undissociated parent anion C6Cl6−, C6Cl5− and Cl− formation. Other fragment anions such as C6Cl4−, C3Cl2−, C2Cl− and Cl2− that undergo complex internal reactions with the temporary negative ion formed after electron transfer account for less than 20% of the total yield. The joint experimental and theoretical methodologies employed in these electron transfer studies provide the most comprehensive and unique assignments of the hexachlorobenzene anionic species and the role of C6Cl6 electronic states in collision induced dissociation to date. [ABSTRACT FROM AUTHOR]

The highest resolution vacuum ultraviolet photoabsorption spectrum of ethyl formate, C2H5OCHO, yet reported is presented over the wavelength range 115.0-215.5 nm (10.15-4.5 eV) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series, observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Calculations have also been carried out to determine the ionization energies and fine structure of the lowest ionic state of ethyl formate and are compared with a newly recorded He(I) photoelectron spectrum (from 10.1 to 16.1 eV). New vibrational structure is observed in the first photoelectron band. The photoabsorption cross sections have been used to calculate the photolysis lifetime of ethyl formate in the upper stratosphere (20-50 km). [ABSTRACT FROM AUTHOR]

We present a compared dynamical study of the S3+(3s23p)2P° + H and P2+(3s23p)2P° + H collision systems involving an accurate ab initio calculation of the potential energy curves and couplings of the molecular states involved in each process followed by a semi-classical collision treatment in the keV laboratory energy range. The results are in good agreement with experiment, when available, and different mechanisms may be pointed out for these reactions in connection with the different molecular interactions involved. © 2007 Wiley Periodicals, Inc. J Quantum Chem, 2007 [ABSTRACT FROM AUTHOR]

Potential energy curves and coupling matrix elements of the one-electron capture by S3+ ions in collision with atomic hydrogen have been determined at the multi-reference configuration interaction level of theory. These calculations show evidence of an untabulated S2+(3s23p3d)3F0 capture level, already pointed out by translational energy spectroscopy experiments, which is necessary to explain the charge transfer mechanism. Calculated cross-sections are in good agreement with the experimental measurements. [Copyright &y& Elsevier]

Athletes need to achieve their optimal level of arousal for peak performance. Visualization or mental rehearsal (i.e., Imagery) often helps to obtain an appropriate level of activation, which can be detected by monitoring Skin Conductance Level (SCL). However, different types of imagery could elicit different amount of physiological arousal. Therefore, this study aims: (1) to investigate differences in SCL associated with two instructional modalities of imagery (guided vs. self-produced) and six different scripts; (2) to check if SCL could differentiate respondents according to their sport expertise. Thirty participants, aged between 14 and 42 years (M = 22.93; SD = 5.24), with different sport levels took part in the study. Participants listened to each previously recorded script and then were asked to imagine the scene for a minute. During the task, SCL was monitored. We analysed the mean value, variance, slope and number of fluctuations per minute of the electrodermal signal. Unsupervised machine learning models were used for measuring the resemblance of the signal. The Wilcoxon signed-rank test was used for distinguishing guided and self-produced imagery, and The Mann-Whitney U test was used for distinguishing results of different level athletes. We discovered that among others, self-produced imagery generates lower SCL, higher variance, and a higher number of fluctuations compared to guided imagery. Moreover, we found similarities of the SCL signal among the groups of athletes (i.e. expertise level). From a practical point of view, our findings suggest that different imagery instructional modalities can be implemented for specific purposes of mental preparation., (© 2024. The Author(s).)

Imagery is a well-known technique in mental training which improves performance efficiency and influences physiological arousal. One of the biomarkers indicating the amount of physiological arousal is skin conductance level (SCL). The aim of our study is to understand how individual differences in personality (e.g. neuroticism), general imagery and situational sport anxiety are linked to arousal measuring with SCL in situational imagery. Thirty participants aged between 14 and 42 years (M = 22.93; SD = 5.24), with sport experience ranging between 2 and 20 years (M = 10.15; SD = 4.75), took part in our study. Participants listened to each previously recorded script and then were asked to imagine the scene for a minute. During the task SCL was monitored using the Biofeedback Expert 2000. Machine learning predictive models based on artificial neural networks have been trained for prediction of physiological response, as a function of selected psychological tests. We found an association among neuroticism, prestart anxiety, and general tendency to use imagery with SCL. From a practical point of view our results may help athletes, coaches, and psychologists to be more aware of the role of individual differences in sport., (© 2023. The Author(s).)

This is the first comprehensive investigation on the anionic species formed during collisions of fast neutral potassium (K) atoms with neutral hexachlorobenzene (C 6 Cl 6 ) molecules in the laboratory frame range from 10 up to 100 eV. In such ion-pair formation experiments we also report a novel K + energy loss spectrum obtained in the forward scattering giving evidence of the most accessible electronic states. The vertical electron affinity of (-3.76 ± 0.20) eV has been obtained and assigned to a purely repulsive transition from the C 6 Cl 6 ground state to a state of the temporary negative ion yielding Cl - formation. These experimental findings are also supported by state-of-the art theoretical calculations on the electronic structure of C 6 Cl 6 in the presence of a potassium atom and are used for analysing the lowest unoccupied molecular orbitals participating in the collision process. From the time-of-flight mass spectra recorded in the wide collision energy range, more than 80% of the total anion yield is due to the undissociated parent anion C 6 Cl 6 - , C 6 Cl 5 - and Cl - formation. Other fragment anions such as C 6 Cl 4 - , C 3 Cl 2 - , C 2 Cl - and Cl 2 - that undergo complex internal reactions with the temporary negative ion formed after electron transfer account for less than 20% of the total yield. The joint experimental and theoretical methodologies employed in these electron transfer studies provide the most comprehensive and unique assignments of the hexachlorobenzene anionic species and the role of C 6 Cl 6 electronic states in collision induced dissociation to date.

The purpose of the current study was to examine the cortical correlates of imagery depending on instructional modality (guided vs. self-produced) using various sports-related scripts. According to the expert-performance approach, we took an idiosyncratic perspective analyzing the mental imagery of an experienced two-time Olympic athlete to verify whether different instructional modalities of imagery (i.e., guided vs. self-produced) and different scripts (e.g., training or competition environment) could differently involve brain activity. The subject listened to each previously recorded script taken from two existing questionnaires concerning imagery ability in sport and then was asked to imagine the scene for a minute. During the task, brain waves were monitored using EEG (32-channel g. Nautilus). Our findings indicate that guided imagery might induce higher high alpha and SMR (usually associated with selective attention), whereas self-produced imagery might facilitate higher low alpha (associated with global resting state and relaxation). Results are discussed in light of the neural efficiency hypothesis as a marker of optimal performance and transient hypofrontality as a marker of flow state. Practical mental training recommendations are presented., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Budnik-Przybylska, Kastrau, Jasik, Kaźmierczak, Doliński, Syty, Łabuda, Przybylski, di Fronso and Bertollo.)

We propose to combine quantum chemical calculations, statistical mechanical methods, and photoionization and particle collision experiments to unravel the redistribution of internal energy of the furan cation and its dissociation pathways. This approach successfully reproduces the relative intensity of the different fragments as a function of the internal energy of the system in photoelectron-photoion coincidence experiments and the different mass spectra obtained when ions ranging from Ar+ to Xe25+ or electrons are used in collision experiments. It provides deep insights into the redistribution of the internal energy in the ionized molecule and its influence on the dissociation pathways and resulting charged fragments. The present pilot study demonstrates the efficiency of a statistical exchange of excitation energy among various degrees of freedom of the molecule and proves that the proposed approach is mature to be extended to more complex systems.

The present work focuses on unraveling the collisional processes leading to the fragmentation of the gas-phase furan molecules under the He + and He 2+ cations impact in the energy range 5-2000 eV. The presence of different mechanisms was identified by the analysis of the optical fragmentation spectra measured using the collision-induced emission spectroscopy (CIES) in conjunction with the ab initio calculations. The measurements of the fragmentation spectra of furan were performed at the different kinetic energies of both cations. In consequence, several excited products were identified by their luminescence. Among them, the emission of helium atoms excited to the 1 s 4 d 1 D 2 , 3 D 1,2,3 states was recorded. The structure of the furan molecule lacks an He atom. Therefore, observation of its emission lines is spectroscopic evidence of an impact reaction occurring via relocation of the electronic charge between interacting entities. Moreover, the recorded spectra revealed significant variations of relative band intensities of the products along with the change of the projectile charge and its velocity. In particular, at lower velocities of He + , the relative cross-sections of dissociation products have prominent resonance-like maxima. In order to elucidate the experimental results, the calculations have been performed by using a high level of quantum chemistry methods. The calculations showed that in both impact systems two collisional processes preceded fragmentation. The first one is an electron transfer from furan molecules to cations that leads to the neutralization and further excitation of the cations. The second mechanism starts from the formation of the He-C 4 H 4 O +/2+ temporary clusters before decomposition, and it is responsible for the appearance of the narrow resonances in the relative cross-section curves.

In this study, novel measurements of negative ion formation in neutral potassium-neutral boronic acid collisions are reported in electron transfer experiments. The fragmentation pattern of phenylboronic acid is comprehensively investigated for a wide range of collision energies, i.e., from 10 to 1000 eV in the laboratory frame, allowing some of the most relevant dissociation channels to be probed. These studies were performed in a crossed molecular beam set up using a potassium atom as an electron donor. The negative ions formed in the collision region were mass analysed with a reflectron time-of-flight mass spectrometer. In the unimolecular decomposition of the temporary negative ion, the two most relevant yields were assigned to BO - and BO 2 - . Moreover, the collision-induced reaction was shown to be selective, i.e., at energies below 100 eV, it mostly formed BO - , while at energies above 100 eV, it mostly formed BO 2 - . In order to further our knowledge on the complex internal reaction mechanisms underlying the influence of the hybridization state of the boron atom, cyclohexylboronic acid was also investigated in the same collision energy range, where the main dissociation channel yielded BO 2 - . The experimental results for phenyl boronic acid are supported by ab initio theoretical calculations of the lowest unoccupied molecular orbitals (LUMOs) accessed in the collision process.

We present a complete exploration of the different fragmentation mechanisms of furan (C 4 H 4 O) operating at low and high energies. Three different theoretical approaches are combined to determine the structure of all possible reaction intermediates, many of them not described in previous studies, and a large number of pathways involving three types of fundamental elementary mechanisms: isomerization, fragmentation, and H/H 2 loss processes (this last one was not yet explored). Our results are compared with the existing experimental and theoretical investigations for furan fragmentation. At low energies the first processes to appear are isomerization, which always implies the breaking of one C-O bond and one or several hydrogen transfers; at intermediate energies the fragmentation of the molecular skeleton becomes the most relevant mechanism; and H/H 2 loss is the dominant processes at high energy. However, the three mechanisms are active in very wide energy ranges and, therefore, at most energies there is a competition among them.

Investigations of collision-induced processes involving carbon ions and molecules of biological interest, in particular DNA building blocks, are crucial to model the effect of radiation on cells in order to improve medical treatments for cancer therapy. Using carbon ions appears to be one of the most efficient ways to increase biological effectiveness to damage cancerous cells by irradiating deep-seated tumors. Therefore, interest in accurate calculations to understand fundamental processes occurring in ion-molecule collision systems has been growing recently. In this context, the charge transfer process in the collision of C 2+ (1s 2 2s 2 ) ions with the heterocyclic sugar moiety building block tetrahydrofuran (THF) was studied in order to interpret the mechanisms occurring at the molecular level. The molecular structure properties of THF were obtained by means of ab initio quantum chemistry methods. The role of the conformational structure and the orientation of the THF molecule in collision with C 2+ ions are particularly discussed. Anisotropic effects of the process dynamics in the collision energy ranging from eV to keV by means of semiclassical treatment are also presented and compared to previous experimental and theoretical investigations. A detailed analysis of the obtained cross sections points out an increase in these values by three orders of magnitude by a change of the THF symmetry from C 2v to C s in collision with C 2+ , which determines a more efficient charge transfer in this case.

The ground state geometries and vibrational frequencies as well as the excitation energies and excited state gradients of the S 1 (nπ*) and S 2 (ππ*) states of trans- and cis-azobenzene are investigated by several DFT methods, namely B3LYP, PBE, M06-2X, CAM-B3LYP, and ωB97X. Excited state properties and in particular gradients are also assessed using the wave function based methods EOM-CCSD and RASPT2/RASSCF. Comparison with experimental data shows that the B3LYP functional gives the most accurate results for the ground state geometry and vibrational frequencies. The analysis of the vertical excitation energies reveals that the RASPT2 approach provides the most accurate excitation energies with deviations of the order of 0.1 eV. Among the TDDFT methods, the CAM-B3LYP functional shows the best performance on the excitation energies. By assessing the excited state gradients with respect to the reference RASPT2 data, the most accurate gradients are obtained with B3LYP, whereas other functionals as well as the EOM-CCSD and RASSCF calculations give less consistent results. Overall, despite the tendency of B3LYP to underestimate the excitation energies, this functional provides the most balanced description of both ground and excited state properties for both isomers of azobenzene in the Franck-Condon region.

A theoretical investigation of the low-energy charge transfer process induced by the S(3+) + H reaction collision is presented. High level ab initio MRCI/CASSCF quantum chemical methods have been used to evaluate the relevant potential energy curves and non-adiabatic couplings. Using the coupled potentials, the dynamics of the system in the few eV energy range has been investigated by means of time-dependent wavepacket propagations. The main channels involved in the process of charge transfer are identified and an approach to follow in real time the electronic density during the collision is introduced., (This journal is © the Owner Societies 2010)