Proton Motion Research Articles

Measurement of apparent diffusion coefficient (ADC) in fetal organs and placenta using 3 Tesla magnetic resonance imaging (MRI) across gestational ages

Diffusion-weighted imaging (DWI) is a technique used to probe the random microscopic motion of water protons in living tissue, represented by a parameter measurement of apparent diffusion coefficient (ADC) values. This study aimed to measure the ADC values of various fetal organs and placenta using 3T at various gestational ages. This was a prospective observational study. A total of 103 singleton pregnancies from 20 to 38 weeks of gestational age were included. Diffusion-weighted imaging was performed in the axial plane from the fetal head to the trunk with the following parameters: TR: 2000–2500 ms; TE: 88 ms; FOV: 250 mm; 256 matrix; slice thickness: 4 mm with a 0 mm gap; acquisition time: 1 min, 18 s. Diffusion gradient values were b = 0 and b = 700 s/mm2. ADC was measured in fetal brain regions (frontal white matter, occipital white matter, centrum semiovale, pons, thalamus, cerebellum, and fetal organs (lungs, kidney, and placenta). ANOVA was used to calculate the mean ADC values. Karl Pearson’s coefficient of correlation was used to evaluate the correlation between ADC values and increasing gestational age. The mean ADC values of brain regions were: frontal white matter (1.64 ± 0.08 × 10− 3 mm2 /s, F-39.10,p-<0.001), occipital white matter (1.64 ± 0.06 × 10− 3 mm2/s, F-26.14, p-<0.001), centrum semiovale (1.62 ± 0.03 × 10− 3 mm2/s, F-49.88,p-<0.001, pons (1.23 ± 0.09 × 10− 3 mm2/s F-9.14,p-<0.001) ), Thalamus (1.21 ± 0.07 × 10− 3 mm2/s, F-13.54,p-<0.001) and cerebellum (1.36 ± 0.10 × 10− 3 mm2 /s, F-4.19,p-<0.001). The mean ADC values of fetal organs were lung (1.92 ± 0.15 × 10− 3 mm2 /s, F-28.24, p-<0.001), kidney (1.34 ± 0.11 × 10− 3 mm2 /s, F-1.05, p- 0.37) and placenta (1.94 ± 0.11 × 10− 3 mm2 /s, F-160.33, p-<0.001). White-matter regions showed a significant positive correlation with increasing gestational age. Statistically, a negative correlation was observed between increasing gestational age and ADC measurements obtained in the thalamus, cerebellum, pons, and kidney. This will be one of the first few studies to provide the ADC values of the fetal brain and fetal organs using 3T MRI. The current study shows that diffusion-weighted MRI can offer a promising technique to evaluate the structural development of fetal organs and can potentially lead to a biomarker for predicting the functionality of the fetal organs in abnormalities.

Consciousness: a quantum optical effect in fluorescent protein pathways

This paper presents a physical mechanism of embodied consciousness based on the dynamic organicity theory. We use the entropic pilot wave theory to describe the quantum dipole oscillations from dipole-bound delocalized (quasi-free) electrons in nonpolar nanocavities of aromatic amino acid residues (benzene moiety /cyclic hydrocarbons that contain resonance structures) and their fluorescent pathways. These pathways contain cavity quasipolariton condensates composed of quantized polarization waves of entangled photons. The behavior of oscillating molecular dipoles is influenced by the quantum nature of dynamic organicity, which causes energy fluctuations necessary to move delocalized electrons and create bare polaritons (quantized polarization waves). These waves correspond to photon quasiparticles interacting with water molecules to form quasipolaritons, softened by interacting with hydroxide ions (OH-) within crystal lattices of interfacial water H30. When [H3O+]=[OH−], the solution is neutral in hydrophobic nanocavities. In such nonpolar cavities, evanescent photons (non-radiative transitions in the absence of any source) are emitted while protons (H+) diffuse due to recombination with hydroxide (OH-) ions, acting as protonic analogs of ‘holes’ or excitons. In protein pores, proton motion strongly coupled with π-electron delocalization is a conduit for exciton-photon (polariton) and its polarization wave component. Internal energy fluctuations comprise both quantum potential energy and negative quantum kinetic energy. We explore how quantum potential energy influences the negentropic effect of a 'repulsive force' guided by entropic pilot waves through pilot wave force (negentropic force), functioning as an information-based action of the polarization wave as a conduit of the cavity quasipolariton. When the rate of change of quantum entropy is zero, and momentum of the polarization wave is zero the internal energy transduction between quantum potential energy to quantum kinetic energy manifests as the negentropic force and facilitates the movement of information-based action for information encoding when negative quantum kinetic energy happens at certain times. Experiments have shown that biphoton entanglement interferes with anaesthetics. We postulate that the disruption of cavity polaritonic condensate through its polarization wave component disrupts the decoding of information, suggesting consciousness is attributed to a quantum optical effect. Therefore, we further theorize that consciousness is attributed to the negative quantum kinetic energy of the polarization wave, which provides an informational structure of multiscale redundancy when negentropic action reduces information redundancy. This has profound implications for understanding consciousness as nonmechanical action channeled through negentropic force when the rate of change of quantum entropy is zero.

Asymmetry in Uranus' High Energy Proton Radiation Belt

AbstractUranus is one of the least explored planets in our solar system, it exhibits a unique magnetic field structure which was observed by NASA's Voyager 2 mission nearly 50 years ago. Notably, Uranus displays extreme magnetic field asymmetry, a feature exclusive to the icy giants. We use the Boris algorithm to investigate how high energy protons behave within this unusual magnetic field, which is motivated by Voyager 2's observation of lower‐than‐expected high energy proton radiation belt intensities at Uranus. When considering full drift motions of high energy protons around Uranus, the azimuthal drift velocity can vary by as much as 15% around the planet. This results in areas around Uranus where particles will be more depleted (faster drift) and other regions where there is a surplus of particles (slower drift). This could provide a partial explanation for the “weak” proton radiation belts observed by Voyager 2.

Mapping Hydrogen Positions along the Proton Transfer Pathway in an Organic Crystal by Computational X-ray Spectra.

Understanding proton transfer (PT) dynamics in condensed phases is crucial in chemistry. We computed a 2D map of N 1s X-ray photoelectron/absorption spectroscopy (XPS/XAS) for an organic donor-acceptor salt crystal against two varying N-H distances to track proton motions. Our results provide a continuous spectroscopic mapping of O-H···N↔O-··· H+-N processes via hydrogen bonds at both nitrogens, demonstrating the sensitivity of N 1s transient XPS/XAS to hydrogen positions and PT. By reducing the O-H length at N1 by only 0.2 Å, we achieved excellent theory-experiment agreement in both XPS and XAS. Our study highlights the challenge in refining proton positions in experimental crystal structures by periodic geometry optimizations and proposes an alternative scaled snapshot protocol as a more effective approach. This work provides valuable insights into X-ray spectra for correlated PT dynamics in complex crystals, benefiting future experimental studies.

Generalized molecule-like structure in atomic nuclei

Starting from a |ϕ|4 field theory with universal pn interacting angular and distance coordinates (θ,r) to depict nuclear long-range correlations, we have derived a cubic Schrödinger equation for NpNnpn interacting virtual bosons, which are believed to dominate the generic evolution of nuclear structure from spherical multi-nucleon shell-model states to deformed collective rotational states. It is shown that two-soliton solution in θ space manifests two opposite pn-type Ising-like chains existing in ground states and their gradual alignment responsible for nuclear rotational excitations. Of particular prominence is two-soliton solution with respect to r: the mutual relative motion of valence protons and neutrons around valence-nucleon mass centers considered as the dynamic equilibrium positions of a non-linear Schrödinger breather. And the resulting non-vanishing root mean square 〈r2〉 divides half the valence nucleons belonging to a chain into four local mass centers and proposes two chain-corresponding molecule-like tetrads outside inert cores pairwise hidden in ground states. Such solitons turn out to be an analogue of opposite axion fluids around a local mass center in the galactic dark-matter halo outside the soliton core (Garnier et al. (2021) [67]) and the present study facilitates making the latter more clear. The generalized molecule-like structure arouses a requisite to the addition of cluster-interior and cluster-to-core electric dipole moments in particular to pear-shaped nuclei, whose variants Schiff moments play an important role in measuring diamagnetic atomic electric dipole moments and therefore understanding CP-violating new physics beyond the standard model. We put additional parts in evidence by befitting the NpNn scheme verified already by electric quadrupole moments in same nuclei.

Elementary Reactions in the Functional Triads of the Blue-Light Photoreceptor BLUF Domain.

The blue light using the flavin (BLUF) domain is one of the smallest photoreceptors in nature, which consists of a unique bidirectional electron-coupled proton relay process in its photoactivation reaction cycle. This perspective summarizes our recent efforts in dissecting the photocycle into three elementary processes, including proton-coupled electron transfer (PCET), proton rocking, and proton relay. Using ultrafast spectroscopy, we have determined the temporal sequence, rates, kinetic isotope effects (KIEs), and concertedness of these elementary steps. Our findings provide important implications for illuminating the photoactivation mechanism of the BLUF domain and suggest an engineering platform to characterize intricate reactions involving proton motions that are ubiquitous in nonphotosensitive protein machines.

Proton Diffusion in Liquid 1,2,3-Triazole Studied by Incoherent Quasi-Elastic Neutron Scattering.

Improving the proton transport in polymer electrolytes impacts the performance of next-generation solid-state batteries. However, little is known about proton conductivity in nonaqueous systems due to the lack of an appropriate level of fundamental understanding. Here, we studied the proton transport in small molecules with dynamic hydrogen bonding, 1,2,3-triazole, as a model system of proton hopping in a nonaqueous environment using incoherent quasi-elastic neutron scattering. By using the jump-diffusion model, we identified the elementary jump-diffusion motion of protons at a much shorter length scale than those by nuclear magnetic resonance and impedance spectroscopy for the estimated long-range diffusion. In addition, a spatially restricted diffusive motion was observed, indicating that proton motion in 1,2,3-triazole is complex with various local correlated dynamics. These correlated dynamics will be important in elucidating the nature of the proton dynamics in nonaqueous systems.

Electronic Fingerprint of the Protonated Imidazole Dimer Probed by X-ray Absorption Spectroscopy.

Protons in low-barrier superstrong hydrogen bonds are typically delocalized between two electronegative atoms. Conventional methods to characterize such superstrong hydrogen bonds are vibrational spectroscopy and diffraction techniques. We introduce soft X-ray spectroscopy to uncover the electronic fingerprints for proton sharing in the protonated imidazole dimer, a prototypical building block enabling effective proton transport in biology and high-temperature fuel cells. Using nitrogen core excitations as a sensitive probe for the protonation status, we identify the X-ray signature of a shared proton in the solvated imidazole dimer in a combined experimental and theoretical approach. The degree of proton sharing is examined as a function of structural variations that modify the shape of the low-barrier potential in the superstrong hydrogen bond. We conclude by showing how the sensitivity to the quantum distribution of proton motion in the double-well potential is reflected in the spectral signature of the shared proton.

Correlated proton dynamics in hydrogen bonding networks: the benchmark case of 3-hydroxyglutaric acid.

Proton and hydrogen-bonded networks sustain a broad range of structural and charge transfer processes in supramolecular materials. The modelling of proton dynamics is however challenging and demands insights from prototypical benchmark systems. The intramolecular H-bonding networks induced by either protonation or deprotonation of 3-hydroxyglutaric acid provide intriguing case studies of correlated proton dynamics. The vibrational signatures associated with the fluxional proton bonding and its coupling with the hydroxyglutaric backbone are investigated here with infrared action ion spectroscopy experiments and Born-Oppenheimer molecular dynamics (BOMD) computations. Despite the formally similar symmetry of protonated and deprotonated hydroxyglutaric acid, the relative proton affinities of the oxygen centers of the carboxylic and carboxylate groups with respect to that of the central hydroxyl group lead to distinct proton dynamics. In the protonated acid, a tautomeric arrangement of the type HOCO·[HOH]+·OCOH is preferred with the proton binding tighter to the central hydroxyl moiety and the electronic density being shared between the two nearly symmetric H-bonds with the carboxylic end groups. In the deprotonated acid, the asymmetric [OCO]-·HO·HOCO configuration is more stable, with a stronger H-bonding on the bare carboxylate end. Both systems display active backbone dynamics and concerted Grothuss-like proton motions, leading to diffuse band structures in their vibrational spectra. These features are accurately reproduced by the BOMD computations.

N → π* Interaction Enabling Transient Inversion of Chirality.

This study reports the observation and characterization of two isomers of the acrolein dimer by using high-resolution rotational spectroscopy in pulsed jets. The first isomer is stabilized by two hydrogen bonds, adopting a planar configuration, and is energetically favored over the second isomer, which exhibits a dominant n → π* interaction in a nearly orthogonal arrangement. Surprisingly, the n → π* interaction was revealed to enable a concerted tunneling motion of two moieties along the carbonyl group. This motion leads to the inversion of transient chirality associated with the exchange of donor-acceptor roles, as revealed by the spectral feature of quadruplets. Inversion of transient chirality is a fundamental phenomenon in quantum mechanics and commonly observed for only inversional motions of protons. It is the first discovery, to the best of our knowledge, that such heavy moieties can also undergo chirality inversion.

The synchrotron photons from the wave solution of the Dirac equation

The goal of this article is to show the derivation of the power spectrum of the synchrotron radiation from the Volkov solution of the Dirac equation and from S-matrix. We also generalize the Bargmann-Michel-Telegdi equation for the spin motion in case it involves the radiation term. This equation plays the crucial role in spin motion of protons in LHC and FERMILAB. The axion production in the magnetic field described by the Volkov solution is discussed.

Denoising of magnetic resonance images of brain tumor using BT-Autonet

While obtaining medical images from sources such as Magnetic Resonance Imaging (MRI), Computed Tomography(CT), and ultrasound, noise is observed within images obtained from real world situations. Often this noise is caused due to vibrations of magnetic coils caused by quick electrical pulses, random thermal motion of protons in the tissue, reverberation and refraction artifacts. Denoising technique is one of the critical aspects in the Computer-aided Diagnosis (CAD) system, since MRI is susceptible to noises like Gaussian, Rician and Rayleigh. Traditional methods for MRI denoising are prone to challenges such as loss of information, loss caused during compression and retention of edge features. Hence, this paper presents a comparative analysis of various image denoising methods and hence, proposes an autoencoder based network Brain Tumor (BT)-Autonet for the removal of noise from brain MRI. Further, the performance analysis of the various denoising approaches is measured using different metrics. The proposed network BT-Autonet for 128 × 128 image dataset achieves a Peak Signal-to-Noise Ratio (PSNR) of 30.788, Mean Square Error(MSE) of 25.179, Structural Similarity Index Measure(SSIM) of 0.9 for Gaussian Dataset. It achieves a PSNR of 27.952, MSE of 23.129, SSIM of 0.861 for Rician Dataset and PSNR of 25.329, MSE of 44.378, SSIM of 0.873 for Rayleigh Dataset with an execution time of 10.5 s for Gaussian Dataset, 11 s for Rician Dataset and 11 s for Rayleigh Dataset. For 256 × 256 image dataset, BT-Autonet achieves a PSNR of 30.452, MSE of 30.036, SSIM of 0.816 for Gaussian Dataset while PSNR of 29.64, MSE of 41.684, SSIM of 0.809 for Rician Dataset and PSNR of 12.818, MSE of 67.219, SSIM 0.279 for Rayleigh Dataset with an execution time of 25 s for Gaussian Dataset, 27 s for Rician Dataset and 26 s for Rayleigh Dataset during the examination. Therefore, the proposed network outperformed the existing models in PSNR, SSIM, MSE and execution time.

Influence of Quantum Effects on Dielectric Relaxation in Functional Electrical and Electric Energy Elements Based on Proton Semiconductors and Dielectrics

Using the quasi-classical kinetic theory of dielectric relaxation, in addition to existing methods, fundamental mathematical expressions are built, which make it possible to more strictly consider the effects of the main charge carriers’ (protons’) tunneling on the numerical values of the molecular parameters (activation energy, equilibrium concentration) of protons in HBC. The formulas for calculating the statistically averaged non-stationary quantum transparency of a parabolic potential barrier for protons have been modernized by more stringent consideration of the effects of corrections caused by an external electric field. For the model of a double-symmetric potential well, a generalized nonlinear solution of the quasi-classical kinetic equation of dielectric relaxation in HBC was built. The phenomenological Bucci-Rive formula for thermally stimulated depolarization current density (TSDC) was first investigated, taking into account quantum transparency, for the case of a parabolic potential barrier. The choice of the parabolic shape of the potential barrier allowed, at a theoretical level, for the mathematical model of relaxation polarization to be brought closer to the conditions of the real spatial structure of the crystal potential field, in comparison with the rectangular potential barrier model. It has been found that quantum effects due to proton tunnel transitions significantly affect the mechanism of thermally stimulated depolarization currents in HBC, over a wide temperature range (50–550 K) and external field parameters (0.1–1 MV/m). Generalized solutions of the nonlinear kinetic equation, recorded considering the effects of field parameters on proton tunnel transitions, made it possible to significantly approximate the theoretical values of activation energies, equilibrium concentrations of protons and amplitudes of the theoretical maxima of the current density of thermally stimulated depolarization, according to their experimental values in the field of low-temperature (50–100 K) and high-temperature (350–550 K) maxima of TSDC density in HBC. For the first time, precision measurements of TSDC temperature spectra were carried out for chalcanthite crystals. The effects of alloying impurities concentrations and crystal calcination temperatures on the parameters of experimental maxima in the TSDC spectrum of chalcanthite were established. A physical mechanism of the quantum tunnel motion of protons in HBC with a complex crystal structure (crystalline hydrates, layered silicates, ferroelectric HBC (KDP, DKDP)) is described. The patterns found in this article indicate a fairly high degree of applied scientific significance for the obtained theoretical results, allowing for the further development of electrophysics and optoelectronics of heterogeneous structures (MIS, MSM) based on proton semiconductors and dielectrics (PSD) and their composites.

Elimination of the bias-stress effect in ligand-free quantum dot field-effect transistors.

Field-effect transistors (FETs) made from colloidal quantum dot (QD) solids commonly suffer from current-voltage hysteresis caused by the bias-stress effect (BSE), which complicates fundamental studies of charge transport in QD solids and the use of QD FETs in electronics. Here, we show that the BSE can be eliminated in n-channel PbSe QD FETs by first removing the QD ligands with a dose of H2S gas and then infilling the QD films with alumina by atomic layer deposition (ALD). The H2S-treated, alumina-infilled FETs have stable, hysteresis-free device characteristics (total short-term stability), indefinite air stability (total long-term stability), and a high electron mobility of up to 14cm2V-1s-1, making them attractive for QD circuitry and optoelectronic devices. The BSE-free devices are utilized to conclusively establish the dependence of the electron mobility on temperature and QD diameter. We demonstrate that the BSE in these devices is caused by both electron trapping at the QD surface and proton drift within the film. The H2S/alumina chemistry produces ligand-free PbSe/PbS/Al2O3 interfaces that lack the traps that cause the electronic part of the BSE, while full alumina infilling stops the proton motion responsible for the ionic part of the BSE. Our matrix engineering approach should aid efforts to eliminate the BSE, boost carrier mobilities, and improve charge transport in other types of nanocrystal solids.

A review of proton migration and interaction energies in doped barium zirconate

Barium zirconate is a promising material for application as solid electrolyte in ceramic fuel cells due to its high protonic conductivity when doped with trivalent oxides such as yttria. On the atomic level, the transport behaviour can be elucidated using density functional theory and energy parameters controlling the mobility have been calculated by several researchers in the last years. In this work, we give a summarizing overview of the available literature data. We consider the interaction energies between protons and dopant ions and the migration barriers of proton motion for individual jumps in bulk BaZrO3 with the focus on Y-doping. Generally, there is a large spread of energy values, which is related to the variations in the calculation parameters and variable distortions in the ionic lattice introduced by defects. Especially the cell size has a paramount influence on the results. In comparison to other dopants, yttrium exhibits a similar trapping of protons in both nearest and second nearest neighbour positions. This seems to be beneficial for conductivity as it leads to overlapping trapping zones and probably moderate barriers for the detrapping jump to the third nearest neighbour position.Based on the collected data, we estimated the protonic conductivity using kinetic Monte Carlo simulations. We applied energy models with different radii of interactions and further varied the energy parameters within the range of literature values. The results show that the interaction radius has only a limited effect while the impact due to the variable energy range is more pronounced. Nevertheless, similar trends are found for all models, especially a minimum in the mobility at low dopant fractions.

Photogrammetry of Ultrafast Excited-State Intramolecular Proton Transfer Pathways in the Fungal Pigment Draconin Red.

Proton transfer processes of organic molecules are key to charge transport and photoprotection in biological systems. Among them, excited-state intramolecular proton transfer (ESIPT) reactions are characterized by quick and efficient charge transfer within a molecule, resulting in ultrafast proton motions. The ESIPT-facilitated interconversion between two tautomers (PS and PA) comprising the tree fungal pigment Draconin Red in solution was investigated using a combination of targeted femtosecond transient absorption (fs-TA) and excited-state femtosecond stimulated Raman spectroscopy (ES-FSRS) measurements. Transient intensity (population and polarizability) and frequency (structural and cooling) dynamics of -COH rocking and -C=C, -C=O stretching modes following directed stimulation of each tautomer elucidate the excitation-dependent relaxation pathways, particularly the bidirectional ESIPT progression out of the Franck-Condon region to the lower-lying excited state, of the intrinsically heterogeneous chromophore in dichloromethane solvent. A characteristic overall excited-state PS-to-PA transition on the picosecond timescale leads to a unique "W"-shaped excited-state Raman intensity pattern due to dynamic resonance enhancement with the Raman pump-probe pulse pair. The ability to utilize quantum mechanics calculations in conjunction with steady-state electronic absorption and emission spectra to induce disparate excited-state populations in an inhomogeneous mixture of similar tautomers has broad implications for the modeling of potential energy surfaces and delineation of reaction mechanisms in naturally occurring chromophores. Such fundamental insights afforded by in-depth analysis of ultrafast spectroscopic datasets are also beneficial for future development of sustainable materials and optoelectronics.

Kelvin–Helmholtz Instability at Mars: In Situ Observations and Kinetic Simulations

Kelvin–Helmholtz (K-H) instability is a fundamental boundary instability between two fluids with different speeds, exchanging the mass, momentum, and energy across the boundary. Although the K-H instability has been suggested to play a critical role in atmospheric ion loss on Mars, the knowledge about its formation and evolution is still poor, due to the limitation of spacecraft missions and a dearth of dedicated simulation codes. In this study, we combine observations from the Mars Atmosphere and Volatile EvolutioN mission and global 3D kinetic simulations to investigate the solar wind–Mars interaction. For the first time, it is found that K-H waves prominently appear in the −E hemisphere, which is attributed to the stronger proton velocity shear therein associated with the asymmetric diamagnetic drift motion of protons. The K-H instability is mainly excited in the −E hemisphere and propagates downstream along the boundary, with the waves also able to be generated near the subsolar point. The K-H waves produce plasma clouds with a net oxygen ion escape rate of about 1.5 × 1024 s−1, contributing to almost half of the global loss on present-day Mars. This heavy ion escape pattern associated with K-H instability is cyclic and could occur on other nonmagnetized planets, potentially influencing planetary atmosphere evolution and habitability.

Hierarchically Macro–Microporous Covalent Organic Frameworks for Efficient Proton Conduction

AbstractAssembling molecular proton carriers into crosslinked networks is widely used to fabricate proton conductors, but they often suffer losses in conduction efficiency and stability accompanied by unclear causes. Covalent organic frameworks (COFs), with well‐defined crystal frameworks and excellent stability, offer a platform for exploring the proton transfer process. Herein, a strategy to construct proton conductors that induce conductivity and stability by introducing bottom‐up hierarchical structure, mass transport interfaces, and host–guest interactions into the COFs is proposed. The proton‐transport platforms are designed to possess hierarchically macro–microporous structure for proton storage and mass transport. The protic ionic liquids, with low proton dissociation energies investigated by DFT calculation, are installed at open channel walls for faster proton motion. As expected, the resultant proton conductors based on a covalent organic framework (PIL0.5@m‐TpPa‐SO3H) with hierarchical pores increase conductivity by approximately three orders of magnitude, achieving the value of 1.02 × 10−1 S cm−1 (90 °C, 100% RH), and maintain excellent stability. In addition, molecular dynamics simulations reveal the mechanism of “hydrogen‐bond network” for proton conduction. This work offers a fresh perspective on COF‐based material manufacturing for high‐performance proton conductors via a protocol of macro‐micropores.

Isotope Effects on Ground and Excited States of Ethyl Cation, H+(C2H4)

The structure and spectra of ethyl cation, H+(C2H4), and its deuterated analogues are investigated using diffusion Monte Carlo (DMC). These calculations all show that the ground state wave function for H+(C2H4) is localized near the minimum energy configuration in which the excess proton is in a bridging configuration, although the amplitude of the vibrational motions of the bridging proton is large. Deuteration of the bridging proton reduces the amplitude of this motion, while deuteration of only the ethylenic hydrogen atoms in H+(C2D4) has little effect on the amplitude of the motion of the bridging proton. Excited states that are accessed by spectroscopically observed transitions in H+(C2H4) are calculated using fixed-node DMC. The calculated and measured frequencies for the states with one quantum of excitation in the ethylenic CH stretching vibrations show good agreement. We also explore the excited state with one quantum of excitation in the proton transfer vibration of the bridging proton and obtain a frequency of 616 cm-1 for H+(C2H4). This frequency increases to 629 cm-1 in H+(C2D4). Deuteration decreases this frequency to 491 and 495 cm-1 in D+(C2H4) and D+(C2D4), respectively. The effects of partial deuteration on the frequencies of the CH stretching vibrations, and the corresponding probability amplitudes are also explored. Finally, we report the vibrationally averaged rotational constants for the four isotopologues of ethyl cation considered in this study.

Forward-backward electron–proton asymmetry from a two-photon crossing of diabatic states of H[formula omitted] in linearly polarized intense laser field

Controlling spatial–temporal overlap between nuclear wave packets propagating on the coupled electronic states with opposite parity by intense laser field leads to a π periodic modulation in the symmetry breaking of the coupled forward–backward electron and proton motions. The most probable directionality of electron and proton moving simultaneously in opposite directions with total electron–proton asymmetry parameter Ae−ptot=0.62 occurs at fixed carrier-envelope phases of ϑ=15° and 195°. Analysis of the time evolution of the nuclear and the electronic-nuclear wave packets on the field-dressed potentials gives rise to newly insightful images of the nonlinear nonperturbative processes for the asymmetrical localization.