Variation Of Dipole Moment Research Articles

Ultralarge Hyperpolarizability, Novel Ladder‐Type Heteroarenes Electro‐Optic Chromophores: Influence of Fused Heterocyclic π‐System and Push–Pull Effect on Nonlinear Optical Properties

ABSTRACTA new series of ladder‐type heteroarenes electro‐optic (EO) chromophores based on unique fused oligothiophene, oligofuran, and oligopyrrole bridge with a strong push–pull effect were designed, and their distinctive electric structure and nonlinear optical (NLO) properties were investigated by multiple methods, including DOS analysis, CPKS method, SOS model, TSM model, and hyperpolarizability density analysis. Interestingly, it is found that the introduction of different strengths of donor and acceptor moieties, the nature of ladder‐type heteroarenes bridge, and the medium polarity play critical roles in achieving ultra‐large hyperpolarizabilities. Encouragingly, the DN1‐6Fu‐AS1 and DN1‐6Py‐AS1 both exhibit ultra‐large βprj values (up to 12965.5 × 10−30 esu) and βtot value (up to 13238.2 × 10−30 esu), owing to their exceptionally low transitions energy and large variation of dipole moment. The DO2‐6Fu‐AO2, DO2‐6Th‐AO2, DO2‐6Fu‐AS1, and DO2‐6Th‐AS1, exhibit very deep HOMO levels, which are expected to have superior air stability and effectively prevent large leakage currents. Hirshfeld surface analysis and interaction region indicator analysis were employed to explore the noncovalent interactions in the dimer. The DO2‐6Fu‐AS1 and DO2‐6Py‐AS1 show the outstanding electro‐optical Pockels effect, and DN1‐6Fu‐AO2 exhibit large SHG responses. These unique and brand‐new push‐pull ladder‐type heteroarenes chromophores are promising candidates for chip‐scale EO modulators, and electronic and photonic devices in emerging communication, energy, analog, and digital technologies.

Revised 4-Point Water Model for the Classical Drude Oscillator Polarizable Force Field: SWM4-HLJ.

In this work the 4-point polarizable SWM4 Drude water model is reparametrized. Multiple models were developed using different strategies toward reproduction of specific target data. Results indicate that no individual model can reproduce all the selected target data in the context of the present form of the potential energy function. The changes considered in the new models include, 1) variations in the gas phase dipole moment, 2) variations in the molecular polarizability, 3) variations of the distance between the oxygen and the M site, 4) variation of the oxygen Lennard-Jones (LJ) parameters, 5) introduction of a LJ potential to the hydrogen atoms, and 6) variations of the H-O-H angle. Detailed analysis is presented for 3 new water models from which a final model, SWM4-HLJ, is selected as the future default model for the Drude polarizable force field. The model maintains the gas phase dipole moment as the experimental value while the remaining listed terms were adjusted including a larger H-O-H angle (108.12). Compared to its predecessor, SWM4-NDP, the self-diffusion coefficient, water dimer properties, and water cluster energies are greatly improved. The temperature dependence of the density of the new model also performs better. Overall, the new SWM4-HLJ water model is a general improvement and a good balance between microscopic and bulk properties is achieved.

Determination of the Dipole Moment Variation Upon Excitation in the Chromophore of Green Fluorescent Protein From Molecular Dynamic Trajectories with QM/MM Potentials Using Machine Learning Methods

Quantum and molecular mechanics (QM/MM) potentials are used to calculate molecular dynamics trajectories for the EYFP protein of the green fluorescent protein family. Machine learning models are constructed to establish the relationship between the geometric parameters of the chromophore in the frame of its trajectory and the properties of its electronic excitation. It is shown that it is not enough to use only bridging bonds between the phenyl and imidazolidone fragments of the chromophore as a geometric parameter, and at least two more neighboring bonds must be added to the model. The proposed models allow determination of the dipole moment variation upon excitation with an average error of 0.11 a.u.

Tailoring Diversified Peripheral Anchor Groups in Spirofluorene‐Dithiolane‐Based Hole Transporting Materials for Efficient Organic and Perovskite Solar Cells from First‐Principle

AbstractThis quantum mechanical approach recommends push–pull molecular engineering to fabricate hole‐transporting materials (HTMs) for photovoltaic cells. It integrates acceptor moieties via thiophene to fluorene core, resulting in five novel HTMs (SFD‐1 to SFD‐5). The results exhibit that derivative HTMs show excellent coherence in excitation, dispersion, and transportation of charge carriers, ensuring robust hole mobility. The anchor moieties functionalized HTMs unveil excellent band alignment with perovskite with fitting HOMO energy levels (−4.93–−5.35 eV), less optical absorption in visible portion ( < 520). This acceptor integration has improved the hole mobility in derivatives, accredited to the smaller hole reorganization energy (0.14–0.68 eV), and greater hole transfer integral (0.22–0.33 eV). The transition density matrix analysis exhibited robust electronic coupling, subtler charge carrier overlapping and greater charge transfer length (7.48–13.73 Å). This resulted in an excellent upsurge in intrinsic charge transference (70.75–92.70%) and smaller exciton binding energy, leading to easier exciton dissociation, and fewer recombination fatalities. However, an adequate variation in dipole moment (4.04 D to 16.34 D) and Gibbs solvation‐free energy (−18.06 to −21.89 kcal mol−1) ensures facile film formation and processability. In conclusion, this approach recommends these flourene‐based HTMs are highly desireable for forthcoming solar cell technology.

Self-assembly mechanism study of Xiaoqu Baijiu in the distillation and condensation stage

ABSTRACT The presented work proposes that the self-assembly of amphiphilic compounds in Xiaoqu Baijiu occurs at the distillation and condensation stage of Chinese Baijiu production for the first time. Such phenomena have similitude with the self-assembly nano-particles conducted by evaporation and condensation approaches. Hydrogen-bonding interactions prompting the formation of molecular clusters in the system. Herein, we characterized the variation of dipole moment, hydrogen bond strength, and cluster morphology in Xiaoqu Baijiu, based on electrochemical impedance spectroscopy, Raman spectroscopy, atomic force microscopy, and molecular dynamics simulation. The effects of major aroma substances on the self-assembly of Xiaoqu Baijiu were fully investigated, it turns out ethyl lactate had the strongest effect on resulting in self-assembled clusters.

Rational Design and Engineering of Terminal Functional Groups in Dibenzothiophene‐Diphenylamine Small Molecular Electron Donors for Enhanced Photovoltaic Efficiency in All‐Small‐Molecule Organic Solar Cells

AbstractAll‐small‐molecule organic solar cells (ASM‐OSCs) offer advantages like well‐defined molecular structures and excellent reproducibility. However, lower photovoltaic efficiencies hinder their adoption due to limitations in designing small molecular electron donors (SMEDs) with optimal energy levels, light absorption, and optoelectronic properties. The present study addresses this gap by rationally designing a series of SMEDs (DBT‐2FA1 to DBT‐2FA6) through terminal acceptors engineering into dibenzothiophene core with diphenylamine side donors for potential applications in ASM‐OSCs. Density functional theory simulations are carried‐out to establish structure‐property relationships based on structural, electrochemical, photophysical, and charge transfer (CT) properties. Results show that the SMEDs exhibit low‐lying HOMOs for suitable energy level alignment with benchmark Y6 acceptor, promoting open‐circuit voltage and charge separation. The panchromatic absorption spectra covering Vis‐NIR region and maximum light harvesting efficiency are beneficial for high current‐density in ASM‐OSCs. Notably, the push‐pull mechanism within SMEDs results in dominant intramolecular CT with above 70% CT excitations. Whereas, a moderate variation in dipole moments and electrostatic potential differences with acceptor material led to 99.9% intermolecular CT, thus ensuring robust exciton dissociation and efficient photocurrent generation. Overall, this work provides a molecular‐level understanding of designing novel SMEDs and their compatibility with acceptor materials for developing future high‐performance ASM‐OSCs.

A tight-binding model for illustrating exciton confinement in semiconductor nanocrystals.

The Brus equation describes the relation between the lowest energy of an electron-hole pair and the size of a semiconductor crystallite. However, taking the strong confinement regime as a starting point, the equation does not cover the transition from weak to strong confinement, the accompanying phenomenon of charge-carrier delocalization, or the change in the transition dipole moment of the electron-hole pair state. Here, we use a one-dimensional, two-particle Hubbard model for interacting electron-hole pairs that extends the well-known tight-binding approach through a point-like electron-hole interaction. On infinite chains, the resulting exciton states exhibit the known relation between the Bohr radius, the exciton binding energy, and the effective mass of the charge carriers. Moreover, by introducing infinite-well boundary conditions, the model enables the transition of the exciton states from weak to strong confinement to be tracked, while straightforward adaptations provide insights into the relation between defects, exciton localization, and confinement. In addition, by introducing the dipole operator, the variation of the transition dipole moment can be mapped when shifting from electron-hole pairs in strong confinement to delocalized and localized excitons in weak confinement. The proposed model system can be readily implemented and extended to different multi-carrier states, thus providing researchers a tool for exploring, understanding, and teaching confinement effects in semiconductor nanocrystals under different conditions.

Pore Fluid Dielectric Constant Effect on Geotechnical and Geo-Environmental Properties of Smectite and Kaolinite

ABSTRACT Organic compounds pose significant environmental concerns, including groundwater contamination. Clays are commonly used as liners to prevent contaminant permeation into the groundwater tables, necessitating an understanding of clay’s behavior in the presence of organic compounds. The presence of organic contaminants results in changes in the dielectric constant of pore fluid, which influences the interparticle energies and double layer thickness in the soil-pore fluid system. This study aims to elucidate the mechanisms of these changes by examining the response of smectite and kaolinite to variations in the dielectric constant. Experimental tests, including Atterberg limits, unconfined compression strength, water adsorption, sedimentation, pH, and XRD, were performed on clay samples at different concentrations of water-isopropyl alcohol mixtures. Results indicate that smectite exhibits higher Atterberg limits and water adsorption capacity compared to kaolinite. Smectite also shows more pronounced changes in response to decreasing dielectric constant. Conversely, changes in kaolinite’s behavior were attributed to variations in pore fluid viscosity and dipole moment. These findings emphasize the importance of considering viscosity and dipole moment alongside dielectric constant in predicting kaolinite behavior. Overall, this study enhances the understanding of how variations in pore fluid dielectric constant affect the geotechnical and geo-environmental behavior of smectite and kaolinite.

Direct observation of charge density and electronic polarization in fluorite ferroelectrics by 4D-STEM

<p>The fluorite ferroelectrics is extremely promising for memory applications due to the silicon compatibility and the robust ferroelectricity with decreasing size. However, the direct observation of local electronic polarization remains elusive, thereby hindering the comprehension of the atomic-scale origin of ferroelectricity. Here, we directly map the real-space charge density of the ZrO<sub>2</sub> nanocrystal in its polar, nonpolar, as well as interphase regions with sub-?ngstr?m resolution by four-dimensional scanning transmission electron microscopy (4D-STEM). Based on the variation of the electric dipole moments, we analyze the electronic contribution to the total spontaneous polarization, which reaches a maximum of 17.8%. In comparison to the continuous polarization in conventional ferroelectric units, the local polarization profile looks like a maple leaf edge at the tetragonal-orthorhombic phase interface, which suggests a gradual increase in the electronic polarization and the covalent nature of the Zr-O bond. We validate these findings with 4D-STEM simulations and calculations based on density functional theory. These findings provide atomic insights into the bonding nature and phase transition feature in fluorite oxides, and unravel the likely origin of ferroelectricity in ferroelectrics.</p>

Study of electronic structure and optical transition properties of low-lying excited states of AuB molecules based on configuration interaction method

High-level configuration interaction method including the spin-orbit coupling is used to investigate the low-lying excited electronic states of AuB that is not reported experimentally. The electronic structure in our work is preformed through the three steps stated below. First of all, Hartree-Fock method is performed to compute the singlet-configuration wavefunction as the initial guess. Next, we generate a multi-reference wavefunction by using the state-averaged complete active space self-consistent field (SACASSCF). Finally, the wavefunctions from CASSCF are utilized as reference, the exact energy point values are calculated by the explicitly correlated dynamic multi-reference configuration interaction method (MRCI). The Davidson correction (+Q) is put forward to solve the size-consistence problem caused by the MRCI method. To ensure the accuracy, the spin-orbit effect and correlation for inner shell electrons and valence shell electrons are considered in our calculation. The potential energy curves of 12 Λ-S electronic states are obtained. According to the explicit potential energy curves, we calculate the spectroscopic constants through solving radial Schrödinger equation numerically. We analyze the influence of electronic state configuration on the dipole moment by using the variation of dipole moment with nuclear distance. The spin-orbit matrix elements for parts of low-lying exciting states are computed, and the relation between spin-orbit coupling and predissociation is discussed. The predissociation is analyzed by using the obtained spin-orbit matrix elements of the 4 Λ-S states which spilt into 12 Ω states. It indicates that due to the absence of the intersections between the curves of spin-orbit matrix elements related with the 4 low-lying Λ-S states, the predissociation for these low-lying exciting states will not occur. Finally, the properties of optical transition between the ground Ω state <inline-formula><tex-math id="M3">\begin{document}$ {\rm A}^{1}{{{\Pi}}}_{1} $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M3.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M3.png"/></alternatives></inline-formula> and first excited Ω state <inline-formula><tex-math id="M4">\begin{document}$ {{\mathrm{X}}}^{1}{{{\Sigma }}}_{{0}^{+}} $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M4.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231347_M4.png"/></alternatives></inline-formula> are discussed in laser-cooling filed by analyzing the Franck-Condon factors and radiative lifetime. And the transition dipole moment is also calculated. But our results reveal that the AuB is not an ideal candidate for laser-cooling. In conclusion, this work is helpful in deepening the understanding of AuB, especially the structures of electronic states, interaction between excited states, and optical transition properties. All the data presented in this paper are openly available at <ext-link ext-link-type="uri" xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="https://www.doi.org/10.57760/sciencedb.j00213.00009">https://www.doi.org/10.57760/sciencedb.j00213.00009</ext-link>.

Boosting charge separation in organic photovoltaics: unveiling dipole moment variations in excited non-fullerene acceptor layers.

The power conversion efficiency (PCE) of organic photovoltaics (OPVs) has reached more than 19% due to the rapid development of non-fullerene acceptors (NFAs). To compete with the PCEs (26%) of commercialized silicon-based inorganic photovoltaics, the drawback of OPVs should be minimized. This drawback is the intrinsic large loss of open-circuit voltage; however, a general approach to this issue remains elusive. Here, we report a discovery regarding highly efficient NFAs, specifically ITIC. We found that charge-transfer (CT) and charge dissociation (CD) can occur even in a neat ITIC film without the donor layer. This is surprising, as these processes were previously believed to take place exclusively at donor/acceptor heterojunctions. Femtosecond time-resolved visible to mid-infrared measurements revealed that in the neat ITIC layers, the intermolecular CT immediately proceeds after photoirradiation (<0.1 ps) to form weakly-bound excitons with a binding energy of 0.3 eV, which are further dissociated into free electrons and holes with a time-constant of 56 ps. Theoretical calculations indicate that stacking faults in ITIC (i.e., V-type molecular stacking) induce instantaneous intermolecular CT and CD in the neat ITIC layer. In contrast, J-type stacking does not support such CT and CD. This previously unknown pathway is triggered by the larger dipole moment change on the excited state generated at the lower symmetric V-type molecular stacking of ITIC. This is in sharp contrast with the need of sufficient energy offset for CT and CD at the donor-acceptor heterojunction, leading to the significant voltage loss in conventional OPVs. These results demonstrate that the rational molecular design of NFAs can increase the local dipole moment change on the excited state within the NFA layer. This finding paves the way for a groundbreaking route toward the commercialization of OPVs.

Facial Construction of Hydroxyl Functional Modified Ultrafine BiPO4 with Variation of Dipole Moment Induced by –OH Group

The hydroxyl groups generated by hydrolysis are grafted onto the surface of BiPO4, and a stable surface hydroxylation structure is formed during the subsequent calcination process. This would facilitate the formation of a new hydroxyl functional structure on the surface of the parent photocatalyst without damaging its intrinsic structure. Synchronous illumination X‐Ray photoelectron spectroscopy shows that the hydroxyl functional ultrafine BiPO4 can realize the conversion of defective oxygen to lattice oxygen, which is more conducive in improving the photocatalytic efficiency. The process of filling hydroxyl oxygen vacancies and forming a stable structure is explored using in‐ situ infrared spectroscopy. The induced dipole moment promotes the separation of photogenerated electron–hole pairs, which is beneficial for the enhancement of photocatalytic activity. The dipole moment of the hydroxyl functional‐modified ultrafine BiPO4 is −1.409 D compared to −1.385 D for ordinary BiPO4. The results of this study indicate that hydroxyl functional structure and reduced sample granularity are effective strategies to improve the photocatalytic performance of BiPO4.

Coherent control of the photonic spin Hall effect by Er3+ ion concentration in an Er3+-doped YAG crystal

We theoretically investigate the effect of doped Er3+ ion concentration on the spin Hall effect (SHE) of light reflected from a Kretschmann-Raether (K-R) structure. In such a structure, an Er3+-doped yttrium aluminum garnet (YAG) crystal acts as the substrate. The excitation of surface plasmon resonance(SPR) leads to the enhancement of the spin splitting of the reflected beam in the resonance reflection dip. Due to the variation of electric dipole moment and energy level lifetime induced by Er3+ ion concentration, the spin-dependent transverse shift is sensitively dependent upon Er3+ ion concentration. Furthermore, under different concentrations of Er3+ ion, the intensity and detuning of the control field have different effects on the magnitude, sign and position of the transverse shift. More importantly, the photonic SHE can be significantly enhanced via choosing the suitable values of the control intensity and detuning at 15% Er3+ ion concentration. Therefore, our scheme may provide a basis for selecting suitable Er3+ ion concentration to enhance the SHE of light in future integrated systems.

Photostable and high-brightness aggregation-induced emission of iridium luminogen achieving reliable and sensitive continuous luminescent quantification of molecular oxygen

Online continuous luminescent oxygen quantification requires both high-brightness luminescence and superior photobleaching resistance of luminogens to afford the requisite level of sensitivity and operational stability, which remains a challenge. Herein, a fluorine-free design strategy of incremental rotors for preparing iridium luminogens with excellent photobleaching resistance and high-brightness aggregation-induced emission (AIE) is presented. The incremental rotors gradually improve the rotational activity of substituents, efficaciously activating the AIE with synchronously improved aggregation-state luminescence efficiency, which is theoretically confirmed by the variations of dipole moments and experimentally verified by the luminescent lifetimes. Moreover, the introduction of triphenylamine significantly improves the photobleaching resistance of iridium luminogens. Subsequently, by optimizing the loading capacity of the iridium luminogen, the improvement of high-brightness AIE on the oxygen sensitivity of ethocel films is successfully observed. Thickness attenuation of ethocel films dramatically shortens the quenching/recovery response to 4.7 s. Importantly, owing to the exceptional photobleaching resistance of the iridium luminogen, distinguished photo-fatigue resistance with operational stability is exhibited by the ethocel film with no luminescence attenuation during 8000 s continuous oxygen quantification.

Spin-orbit coupling effects in the spectroscopy and predissociation of the low-lying states of germanium monobromide

In this work, the electronic structure of GeBr is investigated by high-level multireference configuration interaction (MRCI) method plus Davidson correction (+Q). To improve the accuracy of the computations, the core-valence (CV) electrons correlations, and spin-orbit coupling (SOC) effect are considered. The potential energy curves (PECs) of 23 low-lying states correlated with the lowest three dissociation limits are obtained, as well as those of 45 Ω states originated from the 23 low-lying states. The spectroscopic constants of low-lying states are obtained, which are in agreement with the available experiments. The abrupt variations of dipole moments (DMs) are attributed to the change of the electronic configurations in the avoided crossing regions. Based on the computed PECs of the electronic states and SO matrix elements, the predissociation pathway of the vibrational levels of 4Σ− and 2Π(Ⅲ) sates are discussed. Finally, the transition dipole moments (TDMs), Franck-Condon factors (FCFs), and radiative lifetimes of A2Σ+-X2Π, 2Π(Ⅲ)-X2Π, 1/2(Ⅱ)-X2Π1/2, 1/2(Ⅲ)-X2Π1/2, X2Π3/2-X2Π1/2, and 3/2(Ⅱ)-X2Π1/2 transitions are estimated.

The mechanism of pyroelectricity in polar material hemimorphite

It is known that a crystal structure and symmetry determine the physical properties of materials. Lattice distortion can strongly affect the symmetry of the crystal structure. Polar materials show changes in polarization with temporal fluctuations of temperature due to the asymmetry. As a polar crystal, hemimorphite shows excellent pyroelectric properties. However, to date, there are a few studies on its intrinsic physical properties, and the mechanism of its pyroelectricity remains unclear. In this paper, single-crystal x-ray diffraction measurement was carried out to obtain the atomic positions at 100–400 K. Furthermore, the electric dipole moments of [ZnO4] and [SiO4] polyhedrons along a, b, and c axes have been calculated. The calculated pyroelectric coefficient derived from the intrinsic electric dipole moment was compared with the experimental measurement. The results indicate that the pyroelectric coefficients of hemimorphite at different temperatures mainly come from the variation of the electric dipole moment of [ZnO4] and [SiO4] polyhedrons along the c axis. The electric dipole moment changes as a function of temperature from 100 to 400 K, which is induced by the random lattice distortion. It is found that pyroelectricity is strongly correlated with the random lattice distortion. The establishment of the relationship between lattice distortion and pyroelectricity helps us to regulate the specific electrical parameters of the material, which may lead to future work in energy harvesting and further properties.

Nonlinear Optical Responses of Photoswitchable Donor–Acceptor Stenhouse Adducts

This work combines hyper-Rayleigh scattering (HRS) experiments performed in the NIR range (1.30 and 1.60 μm) and quantum chemical calculations to provide a comprehensive description of the second harmonic generation (SHG) responses of donor-acceptor Stenhouse adducts (DASAs). Representative derivatives of the three generations of DASAs, which differ by the nature of their electron-donating and withdrawing moieties and also include clickable species, have been synthesized and their photoswitching behavior fully characterized. The HRS measurements allow us to establish relationships between the magnitude of the SHG response of open forms and the nature of the donor and acceptor groups. The largest SHG responses are obtained for derivatives incorporating either a barbituric acid or an indanedione acceptor unit, while N-methylaniline appears as the most efficient donor group. The calculations support well the experimental data and show that high hyperpolarizabilities are associated to low excitation energies and large extent of the photoinduced intramolecular charge transfer, which enhances the dipole moment variation between the ground and first dipole-allowed electronic excited state. In addition, a complete investigation of the photoswitching kinetics of DASAs in chloroform solution shows important differences, highlighting in particular the role of the donor group on the photoswitching efficiency.

Seeking for Optimal Excited States in Photoinduced Electron-Transfer Processes─The Case Study of Brooker's Merocyanine.

Material design enters an era in which control of electrons in atoms, molecules, and materials is an essential property to be predicted and thoroughly understood in view of discovering new compounds with properties optimized toward specific optical/optoelectronic applications. π-electronic delocalization and charge separation/recombination enter notably into the set of features that are highly desirable to tailor. Diverse domains are particularly relying on photoinduced electron-transfer (PET), including fields of paramount importance such as energy production through light-harvesting, efficient chemoreceptive sensors, or organic field-effect transistors. In view of completing the arsenal of strategies in this area, we selected Brooker's merocyanine─a typical [D-π-A] compound─as the case study and examined from time-dependent density functional theory the opportunity offered by selected excited states to reach a suited manipulation of the charge transfer (CT) extent. In addition to the consideration of diagnostic tools able to spot the charge amount (i.e., magnitude of electron fraction) transferred upon excitation (qCT), the spatial extent associated with such an electronic transition or CT length (DCT), as well as the corresponding variation in dipole moment between the ground and the excited states (μCT), further analysis of the excitation process was undertaken. The advantage of going beyond the above-mentioned molecular indicators─which can be considered as PET global indices─was explored on the basis of a partitioning of the electron density. Relevant insight was gained on the relation these global indices have with the evolution of (local) features characterizing either chemical bond or electron delocalization upon vertical excitations.

Photoionization of Oriented HD(1Σ+) Yields Vibrating HD+(2Σ+) with Charge Breathing and Small Charge Transfer.

The eigenfunctions of the Hamiltonian associated with the oriented vibrating HD+(2Σ+) ion are calculated beyond the Born-Oppenheimer approximation in the nuclear frame. This makes it possible to study the fully correlated electron-nuclear dynamics of the HD+(2Σ+) after ionization of the HD(1Σ+) molecule. The dynamics is then characterized by the time-dependent probability densities and flux densities of the individual particles, i.e., deuteron, proton, and electron. The flux densities confirm that, although the electric dipole moment changes over time, there is no charge migration, as might be expected from the separation of energy levels of the vibronic states. Instead, the variations of the electric dipole moment over time are caused by small charge transfer and asymmetric charge vibration. Fourier transforms of the time-dependent probability and flux densities uncover the net asymmetric effective potential acting on the electron.

A novel Bayesian approach for disentangling solar and geomagnetic field influences on the radionuclide production rates

Cosmogenic radionuclide records (e.g., 10Be and 14C) contain information on past geomagnetic dipole moment and solar activity changes. Disentangling these signals is challenging, but can be achieved by using independent reconstructions of the geomagnetic dipole moment. Consequently, solar activity reconstructions are directly influenced by the dipole moment uncertainties. Alternatively, the known differences in the rates of change of these two processes can be utilized to separate the signals in the radionuclide data. Previously, frequency filters have been used to separate the effects of the two processes based on the assumption that millennial-scale variations in the radionuclide records are dominated by geomagnetic dipole moment variations, while decadal-to-centennial variations can be attributed to solar activity variations. However, the influences of the two processes likely overlap on centennial timescales and possibly millennial timescales as well, making a simple frequency cut problematic. Here, we present a new Bayesian model that utilizes the knowledge of solar and geomagnetic field variability to reconstruct both solar activity and geomagnetic dipole moment from the radionuclide data at the same time. This method allows for the possibility that solar activity and geomagnetic dipole moment exhibit variations on overlapping timescales. The model was tested and evaluated using synthetic data with realistic noise and then used to reconstruct solar activity and the geomagnetic dipole moment from the 14C production record over the last two millennia. The results agree with reconstructions based on independent geomagnetic field models and with solar activity inferred from the Group Sunspot number. Our Bayesian model also has the potential to be developed further by including additional confounding factors, such as climate influences on the radionuclide records.Graphical