Nonadiabatic Mechanisms Research Articles

Intensity-Borrowing Mechanisms Pertinent to Laser Cooling of Linear Polyatomic Molecules.

A study of the intensity-borrowing mechanisms important to optical cycling transitions in laser-coolable polyatomic molecules arising from non-adiabatic coupling, contributions beyond the Franck-Condon approximation, and Fermi resonances is reported. It has been shown to be necessary to include non-adiabatic coupling to obtain computational accuracy that is sufficient to be useful for laser cooling of molecules. The predicted vibronic branching ratios using perturbation theory based on the non-adiabatic mechanisms have been demonstrated to agree well with those obtained from variational discrete variable representation calculations for representative molecules including CaOH, SrOH, and YbOH. The electron-correlation and basis-set effects on the calculated transition properties, including the vibronic coupling constants, the spin-orbit coupling matrix elements, and the transition dipole moments, and on the calculated branching ratios have been thoroughly studied. The vibronic branching ratios predicted using the present methodologies demonstrate that RaOH is a promising radioactive molecule candidate for laser cooling.

Generalization on Entropy-Ruled Charge and Energy Transport for Organic Solids and Biomolecular Aggregates.

Herein, a generalized version of the entropy-ruled charge and energy transport mechanism for organic solids and biomolecular aggregates is presented. The effects of thermal disorder and electric field on electronic transport in molecular solids have been quantified by entropy, which eventually varies with respect to the typical disorder (static or dynamic). Based on our previous differential entropy (hs)-driven charge transport method, we explore the nonsteady carrier energy flux principle for soft matter systems from small organic solids to macrobiomolecular aggregates. Through this principle, the synergic nature of charge and energy transport in different organic systems is addressed. In this work, entropy is the key parameter to classify whether the carrier dynamics is in a nonsteady or steady state. Besides that, we also propose the formulation for unifying the hopping and band transport, which provides the relaxation time–hopping rate relation and the relaxation time–effective mass ratio. The calculated disorder drift time (or entropy-weighted carrier drift time) for hole transport in an alkyl-substituted triphenylamine (TPA) molecular device is 9.3 × 10–7 s, which illustrates nuclear dynamics-coupled charge transfer kinetics. The existence of nonequilibrium transport is anticipated while the carrier dynamics is in the nonsteady state, which is further examined from the rate of traversing potential in octupolar molecules. Our entropy-ruled Einstein model connects the adiabatic band and nonadiabatic hopping transport mechanisms. The logarithmic current density at different electric field-assisted site energy differences provides information about the typical transport (whether trap-free diffusion or trap-assisted recombination) in molecular devices, which reflects in the Navamani–Shockley diode equation.

Quantum annealing with trigger Hamiltonians: Application to 2-satisfiability and nonstoquastic problems

We study the performance of quantum annealing for two sets of problems, namely, 2-satisfiability (2-SAT) problems represented by Ising-type Hamiltonians and nonstoquastic problems which are obtained by adding extra couplings to the 2-SAT problem Hamiltonians. In addition, we add to the transverse Ising-type Hamiltonian used for quantum annealing a third term, the trigger Hamiltonian with ferromagnetic or antiferromagnetic couplings, which vanishes at the beginning and end of the annealing process. We also analyze some problem instances using the energy spectrum, average energy or overlap of the state during the evolution with the instantaneous low-lying eigenstates of the Hamiltonian, and identify some nonadiabatic mechanisms which can enhance the performance of quantum annealing.

Test Particle Model Predictions of SEP Electron Transport and Precipitation at Mars

AbstractExtreme space weather events can episodically release solar energetic particles (SEPs) that precipitate into planetary atmospheres, leading to aurora and increased ionization. While the induced magnetosphere of Mars does not substantially obstruct SEP protons, the effect on SEP electrons is not known. We use a test particle model modified for relativistic electrons to model transport of 10–200 keV electrons from outside the bow shock and deep in the magnetotail of Mars. We find a substantial influence of curvature and gradient drifts on precipitation, leading to depletions in the bow shock and transport onto closed field lines. The model estimates ∼3% of incident flux precipitates into the Mars atmosphere for a typical SEP event under nominal solar wind conditions, exceeding the estimate from the guiding center path approximation without drift terms. Precipitation is globally patchy. The model estimates 55% of electrons precipitating into cusps along open field lines and 45% precipitating on closed field lines, suggesting drift and nonadiabatic transport mechanisms have a significant influence on precipitation. We also predict that the fraction of precipitating differential flux increases as a function of energy. We discuss how these predictions would be affected by disturbed conditions that tend to accompany the arrival of SEPs and by differing SEP electron spectra hardness and anisotropy. We finally discuss how the simulation predictions compare to observations of diffuse aurora.

Two conductive mechanisms in LaMnO3 thin film: Adiabatic and nonadiabatic small polaronic hopping

We have presented the structural, surface morphology, magnetic and resistivity data for perovskite LaMnO3 epitaxial thin films which are fabricated on well-oriented (001) LaAlO3 substrates by pulsed laser deposition technique. X-ray diffraction [Formula: see text]–[Formula: see text] linear scans and reciprocal space mapping measurement confirm that the out-of-plane and in-plane epitaxial relationship are LMO(001)/LAO(001) and LMO(110)/LAO(110), respectively. Surface roughness determined by atomic force microscopy was no more than 0.3 nm. In the whole studied temperature range, all films only show a paramagnetic behavior instead of any magnetic phase transitions. Correspondingly, the electron transport behaviors always exhibit an insulting state as the temperature changes from high to low. However, we find that none of theoretical models can individually be used to understand their conductive mechanisms. Further studies indicated that charge carries of high and low temperature region obey adiabatic and nonadiabatic small polaronic hopping mechanisms, respectively. This finding offers new ways of exploiting the abnormal ferromagnetism in LaMnO3 multilayer thin films.

Probing the Charge-Transfer Potential Energy Surfaces by the Photodissociation of [Ar-N2

Chemical reaction pathways and product state correlations of gas-phase ion-molecule reactions are governed by the involved potential energy surfaces (PESs). Here, we report the photodissociation dynamics of charge-transfer complex [Ar-N2]+, which is the intermediate of the model system of the Ar+ + N2 → Ar + N2+ reaction. High-resolution recoiling velocity images of photofragmented N2 and N2+ from different dissociation channels exhibit a vibrational state-specific correlation, revealing the nonadiabatic charge-transfer mechanisms upon the photodissociation of [Ar-N2]+. The state-resolved product branching ratios have yielded an accurate determination of the resonant charge-transfer probabilities. This work provides a powerful approach to elucidating the detailed dynamics of chemical events of charge-transfer complex [Ar-N2]+ and to probing the state-to-state charge-transfer PESs.

Nonadiabatic dynamics Mechanisms of natural UV Photoprotection ompounds chlorogenic acid and isochlorogenic acid a: Double conjugated structures but single photoexcited channel

In this work, we proposed the natural molecules chlorogenic acid (CA) and isochlorogenic acid A (ICAA) could be used as sunscreens for the first time. The non-radiative energy relaxation mechanisms of two molecules were presented through a combination of theoretical calculations and spectral experiments. We demonstrated that the trans-cis photoisomerization coordinate in the picosecond timescale could take place in both the natural molecules chlorogenic acid (CA) and isochlorogenic acid A (ICAA). ICAA has a double CA conjugated structure. It has been demonstrated that only one CA conjugated structure in ICAA can be photoexcited. Moreover, the photoisomerization channel of ICAA was similar to CA. We reported a dual conjugated system in a plant-derived sunscreens and the dual conjugated system improves the energy absorption efficiency to some extent. This work confirmed that the plant-derived CA and ICAA could be potential natural sunscreen molecules and created an avenue for designing novel sunscreen compounds.

Vibrationally inelastic scattering of HCl from Ag(111).

Using molecular beam cooled samples and quantum state-selective detection, we observe v = 0 → 1 vibrational transitions when HCl (v = 0) collides with an Ag(111) surface and derive both the incidence energy and surface temperature dependence of the transition probability. Our observations reveal that both electronically adiabatic and non-adiabatic mechanisms are at play in this inelastic process. A comparison to other systems shows similarities and trends that are consistent with an electron transfer mechanism forming a transient HCl-. For example, the electronically nonadiabatic coupling is stronger than for HCl scattering from Au, where the solid's work function is higher. HCl differs from other systems in that dissociation is possible over a low barrier. Vibrationally inelastic v = 1 → 2 transitions could not be seen when HCl (v = 1) collides with an Ag(111) surface. We suggest that scattering events, where HCl (v = 1) is subject to dynamical influences that increase its vibrational energy, lead efficiently to dissociation before the HCl (v = 2) molecule can escape the surface. This system appears to be an excellent candidate to study electronically nonadiabatic effects in dissociative adsorption.

Perspectives on Dye Sensitization of Nanocrystalline Mesoporous Thin Films.

Recent advances in our mechanistic understanding of dye-sensitized electron transfer reactions occurring at metal oxide interfaces are described. These advances were enabled by the advent of mesoporous thin films, comprised of anatase TiO2 nanocrystallites, that are amenable to spectroscopic and electrochemical characterization in unprecedented molecular-level detail. The metal-to-ligand charge transfer (MLCT) excited states of Ru polypyridyl compounds serve as the dye sensitizers. Excited-state injection often occurs on ultrafast time scales with yields that can be tuned from unity to near zero through modification of the sensitizer or the electrolyte composition. Transport of the injected electron and the oxidized sensitizer (hole hopping) are both operative in the composite mechanism for charge recombination between the injected electron and the oxidized sensitizer. Sensitizers that contain a pendant electron donor, as well as core/shell SnO2/TiO2 nanostructures, often prolong the lifetime of the injected electron and provide fundamental insights into adiabatic and nonadiabatic electron transfer mechanisms. Regeneration of the oxidized sensitizer by iodide is enhanced through halogen bonding, orbital pathways, and ion pairing. A substantial ∼10 MV cm-1 electric field is created by electron injection into TiO2 nanocrystallites that induces ion migration, reports on the sensitizer dipole orientation, and (in some cases) reorients or flips the sensitizer. Dye-sensitized conductive oxides also promote long-lived charge separation with bias dependent kinetics that provide insights into the reorganization energies associated with electron and proton-coupled electron transfer in the electric double layer.

Quantum Approximate Optimization Algorithm: Performance, Mechanism, and Implementation on Near-Term Devices

The Quantum Approximate Optimization Algorithm (QAOA) is a hybrid quantum-classical variational algorithm designed to tackle combinatorial optimization problems. Despite its promise for near-term quantum applications, not much is currently understood about QAOA's performance beyond its lowest-depth variant. An essential but missing ingredient for understanding and deploying QAOA is a constructive approach to carry out the outer-loop classical optimization. We provide an in-depth study of the performance of QAOA on MaxCut problems by developing an efficient parameter-optimization procedure and revealing its ability to exploit non-adiabatic operations. Building on observed patterns in optimal parameters, we propose heuristic strategies for initializing optimizations to find quasi-optimal $p$-level QAOA parameters in $O(\text{poly}(p))$ time, whereas the standard strategy of random initialization requires $2^{O(p)}$ optimization runs to achieve similar performance. We then benchmark QAOA and compare it with quantum annealing, especially on difficult instances where adiabatic quantum annealing fails due to small spectral gaps. The comparison reveals that QAOA can learn via optimization to utilize non-adiabatic mechanisms to circumvent the challenges associated with vanishing spectral gaps. Finally, we provide a realistic resource analysis on the experimental implementation of QAOA. When quantum fluctuations in measurements are accounted for, we illustrate that optimization will be important only for problem sizes beyond numerical simulations, but accessible on near-term devices. We propose a feasible implementation of large MaxCut problems with a few hundred vertices in a system of 2D neutral atoms, reaching the regime to challenge the best classical algorithms.

Magnetotail dipolarization fronts and particle acceleration: A review

In this paper, the particle acceleration processes around magnetotail dipolarization fronts (DFs) were reviewed. We summarize the spacecraft observations (including Cluster, THEMIS, MMS) and numerical simulations (including MHD, test-particle, hybrid, LSK, PIC) of these processes. Specifically, we (1) introduce the properties of DFs at MHD scale, ion scale, and electron scale, (2) review the properties of suprathermal electrons with particular focus on the pitch-angle distributions, (3) define the particle-acceleration process and distinguish it from the particle-heating process, (4) identify the particle-acceleration process from spacecraft measurements of energy fluxes, and (5) quantify the acceleration efficiency and compare it with other processes in the magnetosphere (e.g., magnetic reconnection and radiation-belt acceleration processes). We focus on both the acceleration of electrons and ions (including light ions and heavy ions). Regarding electron acceleration, we introduce Fermi, betatron, and non-adiabatic acceleration mechanisms; regarding ion acceleration, we present Fermi, betatron, reflection, resonance, and non-adiabatic acceleration mechanisms. We also discuss the unsolved problems and open questions relevant to this topic, and suggest directions for future studies.

Adiabatic and nonadiabatic charge separation dynamics in graphene oxide quantum dots for overall water splitting

Chemical functionalization and heteroatom doping are two effective strategies for improving the conductivity of a graphene lattice. Nitrogen-doped graphene oxide quantum dot (GOQD) has been reported to possess both p- and n-conductivity that is induced by an oxygen functional group and nitrogen doping, respectively, and is suitable for catalyzing hydrogen and oxygen evolution reactions for complete water splitting. The experimental study shows that the hydrogen evolution reaction occurs considerably faster than the oxygen evolution reaction. However, the mechanism of this phenomenon remains unknown, which poses a challenge to the chemical modification of such classes of materials. In the present work, we perform nonadiabatic ab initio molecular dynamics to explore the charge separation dynamics in N-doped GOQD with oxygen functional groups. Our results show that there exists multiple charge decay channels governed by different mechanisms, which complicates the overall charge separation dynamics in N-doped GOQD. The intramolecular electron transfer mainly occurs through the nonadiabatic channel, whereas the intramolecular hole transfer mainly occurs through the adiabatic channel. There is an additional adiabatic decay channel in the p-domain, which accelerates electron–hole recombination in the p-domain. We further calculated the decoherence times and found that the decoherence of intramolecular electron transfer occurs considerably faster than that of hole transfer, which slows the quantum transition of intramolecular electron transfer. Finally, we simulated the carrier relaxation times and found that the electron relaxation is approximately one order of magnitude longer than that of the hole relaxation. Our calculation rationalizes the experimentally observed higher catalytic activity towards the hydrogen evolution compared to the oxygen evolution. More importantly, the calculation explains the fundamental roles of nitrogen doping and oxygen functional groups in the adiabatic and nonadiabatic charge decay mechanisms.

Electron radiation belt dynamics during magnetic storms and in quiet time

The paper discusses the dynamics of the outer electron belt, adiabatic and nonadiabatic mechanisms of replenishment and losses of energetic electrons. Under undisturbed conditions, the outer electron belt gradually empties: in the inner magnetosphere due to electron precipitation in the atmosphere and in the quasi-trapping region due to losses at the magnetopause because drift shells of electrons are not closed there. The latter process does not occur in normal years due to the masking replenishment by freshly accelerated particles, but in years of extremely low activity it leads to a significant decrease in the electron population of the belt. During the magnetic storm main phase, the first reason for the decrease in the electron flux intensity is the adiabatic cooling associated with conservation of adiabatic invariants and complemented by precipitation of electrons into the atmosphere and their dropout at the magnetopause. Electron flux increases involve EB electron injection by the induction electric field of substorm activation and by the large-scale solar wind electric field, with pitch energy diffusion along with adiabatic heating in the recovery phase. The rate of electron flux recovery after a storm is determined by the ratio of nonadiabatic increases and losses; hence the electron flux represents a continuous series from low to very high values. The combination of these processes determines the individual character of radiation belt development during each magnetic storm and the behavior of the belt in the quiet time.

Динамика электронного радиационного пояса во время магнитных возмущений и в спокойное время

The paper discusses the dynamics of the outer electron belt, adiabatic and nonadiabatic mechanisms of replenishment and losses of energetic electrons. Under undisturbed conditions, the outer electron belt gradually empties: in the inner magnetosphere due to electron precipitation in the atmosphere and in the quasi-trapping region due to losses at the magnetopause because drift shells of electrons are not closed there. The latter process does not occur in normal years due to the masking replenishment by freshly accelerated particles, but in years of extremely low activity it leads to a significant decrease in the electron population of the belt. During the magnetic storm main phase, the first reason for the decrease in the electron flux intensity is the adiabatic cooling associated with conservation of adiabatic invariants and complemented by precipitation of electrons into the atmosphere and their dropout at the magnetopause. Electron flux increases involve EB electron injection by the induction electric field of substorm activation and by the large-scale solar wind electric field, with pitch energy diffusion along with adiabatic heating in the recovery phase. The rate of electron flux recovery after a storm is determined by the ratio of nonadiabatic increases and losses; hence the electron flux represents a continuous series from low to very high values. The combination of these processes determines the individual character of radiation belt development during each magnetic storm and the behavior of the belt in the quiet time.

Double photoionization of propylene oxide: A coincidence study of the ejection of a pair of valence-shell electrons.

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality. In the present work, a photoelectron-photoion-photoion coincidence technique, using an ion-imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV energy range, permits us (i) to observe six double ionization fragmentation channels, their relative yields being accounted for about two-thirds by the couple (C2H4+, CH2O+) and one-fifth by (C2H3+, CH3O+); (ii) to measure thresholds for their openings as a function of photon energy; and (iii) to unravel a pronounced bimodality for a kinetic-energy-released distribution, fingerprint of competitive non-adiabatic mechanisms.

Strong Interaction at the Perovskite/TiO2 Interface Facilitates Ultrafast Photoinduced Charge Separation: A Nonadiabatic Molecular Dynamics Study

Interfacial electron transfer (ET) plays a key role in the operation of solar cells based on TiO2 sensitized with organohalide perovskites, since it leads to separation of the photogenerated electrons and holes into different materials. The reported experimental ET times range by over 3 orders of magnitude, from sub-200 fs to over 300 ps. Using nonadiabatic molecular dynamics combined with ab initio time-domain density functional theory, we demonstrate that ET at a CH3NH3PbI3/TiO2 interface can be complete within 100 fs, indicating that the longer time scales reflect other processes, such as charge and exciton diffusion in perovskite bulk. The electron injection is fast because the interaction between the donor and acceptor species is strong at ambient conditions. Photoexcitation directly at the interface can create a charge-separated state. Electrons generated farther away inject by a combination of adiabatic and nonadiabatic mechanisms. Thermally activated low frequency vibrational motions at the interf...

Ion pair formation in the NeAr dimer irradiated by monochromatic soft X-rays

We investigated Ne+–Ar+ ion-pair formation which follows irradiation of the NeAr dimer by monochromatic soft X-rays. Using momentum-resolved electron-ion multicoincidence spectroscopy, we could unambiguously identify that the formation of the ion pair at photon energy of 200.5eV proceeds via interatomic Coulombic decay (ICD) of the Ne+(2s−1)Ar inner-valence ionized and NeAr+(3p−25d) ionization satellite states. Photoabsorption at higher photon energies of 268.2eV and 888.7eV leads to the emission of core electrons of Ar and Ne respectively, and to the subsequent local Auger decay process. We demonstrate that at these energies the ion pair formation originating in the doubly ionized Ar L-MM and Ne K-LL Auger final states proceeds mostly via radiative charge transfer and charge transfer driven by non-adiabatic coupling mechanisms.

Prediction of electronically nonadiabatic decomposition mechanisms of isolated gas phase nitrogen-rich energetic salt: Guanidium-triazolate

Electronically nonadiabatic decomposition pathways of guanidium triazolate are explored theoretically. Nonadiabatically coupled potential energy surfaces are explored at the complete active space self-consistent field (CASSCF) level of theory. For better estimation of energies complete active space second order perturbation theories (CASPT2 and CASMP2) are also employed. Density functional theory (DFT) with B3LYP functional and MP2 level of theory are used to explore subsequent ground state decomposition pathways. In comparison with all possible stable decomposition products (such as, N2, NH3, HNC, HCN, NH2CN and CH3NC), only NH3 (with NH2CN) and N2 are predicted to be energetically most accessible initial decomposition products. Furthermore, different conical intersections between the S1 and S0 surfaces, which are computed at the CASSCF(14,10)/6-31G(d) level of theory, are found to play an essential role in the excited state deactivation process of guanidium triazolate. This is the first report on the electronically nonadiabatic decomposition mechanisms of isolated guanidium triazolate salt.

Electronically nonadiabatic decomposition mechanisms of clusters of zinc and dimethylnitramine

Electronically nonadiabatic decomposition mechanisms of dimethylnitramine (DMNA) in presence of zinc metal clusters are explored. Complete active space self-consistent field (CASSCF) calculation is employed for DMNA–Zn and ONIOM (Our own N-layered integrated molecular orbital and molecular mechanics) methodology is coupled with CASSCF methodology for DMNA–Zn10 cluster. Present computational results show that DMNA–Zn clusters undergo electronically nonadiabatic reactions, rendering nitro-nitrite isomerization followed by NO elimination. The overall reactions are also found to be highly exothermic in nature. This is the first report on electronically nonadiabatic decomposition pathways of DMNA–Znn neutral clusters.

Nonadiabatic reaction mechanisms of the O(3P) with cyclopentene

The reaction mechanism of the ground state oxygen atom O(3P) with cyclopentene is investigated theoretically. The triplet and singlet potential energy surfaces are calculated at the CCSD(T)//MP2/6-311G(d,p) level and the minimum energy crossing points (MECPs) between the two surfaces are located by means of the Newton–Lagrange method, from which the complex nonadiabatic reaction pathways are revealed. Based on the theoretical results, the most probable reaction mechanism of O(3P) with c-C5H8 is described, which agrees with the experimental results nicely, including the condensed phase experiment. At the same time, the newly revealed reaction mechanism clarifies the previous controversial product distribution, and predicts the possible existence of the new enol product, cyclopentenol.