Nonadiabatic Transitions Research Articles

Nonadiabatic ab initio chemical reaction dynamics for the photoisomerization reaction of 3,5-dimethylisoxazole via the S1 electronic state.

Nonadiabatic ab initio molecular dynamics simulations were performed to explore the photoisomerization pathway from isoxazole (iso-OXA) to oxazole (OXA), considering four electronic states. The XMS-CASPT2 and SA4-CASSCF theories were employed to describe these electronic structures, which were caused by 12 electrons in 11 orbitals with the cc-pVDZ + sp diffuse basis set; the Gaussian s- and p-type diffuse functions were extracted from Dunning's aug-cc-pVDZ function. The potential energy and its gradient at each time step were computed on-the-fly at these levels in the time evolution of the classical trajectory. When the two electronic states were close to each other, the trajectory surface hopping (TSH) judgment between the two adjacent states was carried out by the anteater procedure based on the Zhu-Nakamura formula (ZN-TSH). The two different excited state lifetimes were found to exist in the first electronic state (S1), estimated at 10.77 and 119.81 fs. Upon photoexcitation, the N-O bond breaks and energetically relaxes to the ground state (S0). In the pathway leading to the main product, azirine formation, the 5-membered ring retains a planar structure while undergoing a non-adiabatic transition with an increasing N-O bond distance. Furthermore, it was verified that a 1,2-shift takes place in the pathway that results in the production of ketenimine, causing a nonadiabatic transition.

Nonadiabatic Excited-State Molecular Dynamics with an Explicit Solvent: NEXMD-SANDER Implementation.

In this article, the nonadiabatic excited-state Molecular dynamics (NEXMD) package is linked with the SANDER package, provided by AMBERTOOLS. The combination of these software packages enables the simulation of photoinduced dynamics of large multichromophoric conjugated molecules involving several coupled electronic excited states embedded in an explicit solvent by using the quantum/mechanics/molecular mechanics (QM/MM) methodology. The fewest switches surface hopping algorithm, as implemented in NEXMD, is used to account for quantum transitions among the adiabatic excited-state simulations of the photoexcitation and subsequent nonadiabatic electronic transitions, and vibrational energy relaxation of a substituted polyphenylenevinylene oligomer (PPV3-NO2) in vacuum and methanol as an explicit solvent has been used as a test case. The impact of including specific solvent molecules in the QM region is also analyzed. Our NEXMD-SANDER QM/MM implementation provides a useful computational tool to simulate qualitatively solvent-dependent effects, like electron transfer, stabilization of charge-separated excited states, and the role of solvent reorganization in the molecular optical properties, observed in solution-based spectroscopic experiments.

Fast singlet excited-state deactivation pathway of flavin with a trimethoxyphenyl derivative

Incorporation of the trimethoxyphenyl group at position 7 of flavin can drastically change the photophysical properties of flavin. We show unique fast singlet 1(π,π*) excited state deactivation pathway through nonadiabatic transition to the 1(n,π*) excited- state, and subsequent deactivation to the ground electronic state (S0), closing the photocycle. This mechanism explains the exceptionally weak fluorescence and the short excited–state lifetime for the flavin trimethoxyphenyl derivative and the lack of excited triplet T1 state formation. Full recovery of flavin in its ground state takes place within a 15 ps time window after photoexcitation in a polar solvent such as acetonitrile. According to quantum chemical calculations, the C(2)-O distance elongates by 0.16 Å in the 1(n,π*) state, with respect to the ground state. Intermediate–state structures are predicted by theoretical ab initio calculations and their dynamics are investigated using broadband vis-NIR time-resolved transient absorption and fluorescence up-conversion techniques.

Observation of reversible conformational interconversion accompanied by 3p internal conversions in Rydberg-excited N,N-dimethylethylamine

Conformational dynamics has been well observed in the 3s Rydberg state of amines, whereas its observation in higher-energy, non-equilibrium 3p Rydberg states is very rare, especially for a reversible conformational transition that could compete with other non-adiabatic transitions. Herein, we report the observation of a reversible conformational interconversion phenomenon in the 3p Rydberg excited-state dynamics of N,N-dimethylethylamine (DMEA). Upon electronic excitation, a forward and backward interconversion between the initially prepared 3p_l and 3p_h conformers accompanied by 3p internal conversions occurs, resulting in a 3p_l/3p_h equilibrium ratio of 61 %/39 % within ∼1.5 ps. The ensuing parallel internal conversions from the 3p_l to 3s_l and 3p_h to 3s_h deposit about 1.80 eV of vibrational energy into the 3s state, enabling a fast conformational interconversion between the 3s_h and 3s_l conformers to proceed within ∼2.0 ps. The final 3s_l/3s_h equilibrium ratio was determined to be 76 %/24 %. This work presents a real-time observation of the entire conformational interconversion process initiating from the higher-energy 3p states and finally reaching an equilibrium on the lower-energy 3s state.

Alternative fast quantum logic gates using nonadiabatic Landau-Zener-Stückelberg-Majorana transitions

A conventional realization of quantum logic gates and control is based on resonant Rabi oscillations of the occupation probability of the system. This approach has certain limitations and complications, like counter-rotating terms. We study an alternative paradigm for implementing quantum logic gates based on Landau-Zener-Stückelberg-Majorana (LZSM) interferometry with nonresonant driving and the alternation of adiabatic evolution and nonadiabatic transitions. Compared to Rabi oscillations, the main differences are a nonresonant driving frequency and a small number of periods in the external driving. We explore the dynamics of a multilevel quantum system under LZSM drives and optimize the parameters for increasing the gate speed. We define the parameters of the external driving required for implementing a specific quantum logic gate using the adiabatic-impulse model. In particular, we demonstrate the implementations of single-qubit X, Y, Hadamard gates, and two-qubit i and gates using the LZSM transitions. The considered LZSM approach for implementing arbitrary quantum logic gates can be applied to a large variety of multilevel quantum systems and external driving. Published by the American Physical Society 2024

Sculpting of Exoplanetary Systems Driven by a Misaligned Disk and Stellar Oblateness: Origin of Perpendicular Orbits in HD 3167

A significant proportion of exoplanets have been detected with highly tilted or even polar orbits relative to their host stars’ equatorial planes. These unusual orbital configurations are often linked to postdisk secular interactions among multiple bodies. However, many aspects remain elusive. In this study, we investigate the role of disk-induced spin–orbit misalignments in shaping the architecture of multiplanet systems, taking into account the combined effect of the host star’s oblateness and the full-space disk potential. We demonstrate that large mutual planetary inclinations can arise from a saddle-center bifurcation occurring during the photoevaporation of the disk. This bifurcation triggers an instant, nonadiabatic transition in the planet’s libration. Following this process, the orbital evolution diverges into several distinct patterns. Notably, in scenarios involving a near-polar primordial misalignment, the orbit, consistently librating about a coplanar equilibrium axis, can be captured by an orthogonal equilibrium during the decay of the stellar oblateness. However, the orbit will be eventually recaptured by the coplanar equilibrium, aligned or antialigned with the orientation of the outer orbit, resulting in either a prograde or retrograde inner–outer orbit configuration. Additionally, general relativity contributes to maintaining eccentricity stability within these dynamic scenarios. Through the proposed mechanism, we can provide a plausible explanation for the unique, near-perpendicular, and likely retrograde orbit architecture observed in the HD 3167 system, enhancing our understanding of exoplanetary system dynamics.

Photochromic reaction pathways of 1,1′-azobis-1,2,3-triazole: A CASSCF and spin-flip DFT study

This study employed multiconfigurational CASSCF and MS-CASPT2 methods to investigate the photoinduced isomerization mechanism of 1,1′-azobis-1,2,3-triazole. The MS-CASPT2//CASSCF computational results indicate that the photoisomerization reaction of 1,1′-azobis-1,2,3-triazole involves a non-adiabatic transition pathway through the S2 state. After photoexcitation to the S2 state, the molecule undergoes internal conversion to reach S1-min, followed by a non-radiative transition back to the ground state. The S1/S0-CI and S1-min have similar structures and close energies, which facilitates unidirectional rotation. The weak coupling between the ground state and excited states may be due to the strong electron-withdrawing nature of the N8 chain. Additionally, using the MS-CASPT2//CASSCF computational results as a reference, we compared the differences in describing the photoisomerization process of this compound using the SF-DFT method, both qualitatively and quantitatively. The results demonstrate that the SF-DFT method significantly underestimates the energy of the S1 state. These findings are expected to deepen the understanding of non-adiabatic transitions in the photoinduced rotation of high-nitrogen compounds and provide theoretical insights for other high-nitrogen compounds that may exhibit photochromism.

Transport and fusion of Majorana zero modes in the presence of nonadiabatic transitions

Transport and fusion of Majorana zero modes in the presence of nonadiabatic transitions

Diabatic Potential Energy Surfaces of SrH2+ and Dynamics Studies of the Sr+(5s2S) + H2 Reaction.

Based on the ab initio energy points of both ground and excited states, a neural network fitting method combined with a specific function was successfully used to construct the diabatic potential energy surfaces (PESs) of the SrH2+ system. The topographical features of the diabatic PESs were examined in detail. The results indicate that the nonadiabatic transition characteristics between ground and excited states are accurately described by the newly constructed diabatic PESs. To verify the validity and applicability of the diabatic PESs, as well as the nonadiabatic effects during the reaction process, the quantum dynamics studies of the Sr+(5s2S) + H2 reaction were performed based on both adiabatic and diabatic PESs. The dynamics results indicate that adiabatic dynamics results are dozens of times larger than those of nonadiabatic. This illustrates the significant effect of nonadiabaticity, indicating that adiabatic dynamics results often overestimate the actual values. The integral cross sections (ICSs) were calculated and compared with the experimental data. The diabatic ICSs are in good agreement with the experimental results. The reasonable dynamics results indicate that the newly constructed diabatic PESs are suitable for the relevant dynamics studies.

Conical Intersections at Interfaces Revealed by Phase-Cycling Interface-Specific Two-Dimensional Electronic Spectroscopy (i2D-ES).

Conical intersections (CIs) hold significant stake in manipulating and controlling photochemical reaction pathways of molecules at interfaces and surfaces by affecting molecular dynamics therein. Currently, there is no tool for characterizing CIs at interfaces and surfaces. To this end, we have developed phase-cycling interface-specific two-dimensional electronic spectroscopy (i2D-ES) and combined it with advanced computational modeling to explore nonadiabatic CI dynamics of molecules at the air/water interface. Specifically, we integrated the phase locked pump pulse pair with an interface-specific electronic probe to obtain the two-dimensional interface-specific responses. We demonstrate that the nonadiabatic transitions of an interface-active azo dye molecule that occur through the CIs at the interface have different kinetic pathways from those in the bulk water. Upon photoexcitation, two CIs are present: one from an intersection of an optically active S2 state with a dark S1 state and the other from the intersection of the progressed S1 with the ground state S0. We find that the molecular conformations in the ground state are different for interfacial molecules. The interfacial molecules are intimately correlated with the locally populated excited state S2 being farther away from the CI region. This leads to slower nonadiabatic dynamics at the interface than in bulk water. Moreover, we show that the nonadiabatic transition from the S1 dark state to the ground state is significantly longer at the interface than that in the bulk, which is likely due to the orientationally restricted configuration of the excited state at the interface. Our findings suggest that orientational configurations of molecules manipulate reaction pathways at interfaces and surfaces.

Theory for proton-coupled energy transfer.

In the recently discovered proton-coupled energy transfer (PCEnT) mechanism, the transfer of electronic excitation energy between donor and acceptor chromophores is coupled to a proton transfer reaction. Herein, we develop a general theory for PCEnT and derive an analytical expression for the nonadiabatic PCEnT rate constant. This theory treats the transferring hydrogen nucleus quantum mechanically and describes the PCEnT process in terms of nonadiabatic transitions between reactant and product electron-proton vibronic states. The rate constant is expressed as a summation over these vibronic states, and the contribution of each pair of vibronic states depends on the square of the vibronic coupling as well as the spectral convolution integral, which can be viewed as a generalization of the Förster-type spectral overlap integral for vibronic rather than electronic states. The convolution integral also accounts for the common vibrational modes shared by the donor and acceptor chromophores for intramolecular PCEnT. We apply this theory to model systems to investigate the key features of PCEnT processes. The excited vibronic states can contribute significantly to the total PCEnT rate constant, and the common modes can either slow down or speed up the process. Because the pairs of vibronic states that contribute the most to the PCEnT rate constant may correspond to spectroscopically dark states, PCEnT could occur even when there is no apparent overlap between the donor emission and acceptor absorption spectra. This theory will assist in the interpretation of experimental data and will guide the design of additional PCEnT systems.

Implementation of Nonadiabatic Molecular Dynamics for Intersystem Crossing Based on a Time-Dependent Density-Functional Tight-Binding Method.

Intersystem crossing (ISC) and internal conversion (IC) are types of nonadiabatic transitions that play important roles in a wide range of fields, including photochemistry, photophysics, and photobiology. The nonadiabatic molecular dynamics (NA-MD) method is a powerful tool for computational simulations of dynamic phenomena involving nonadiabatic transitions. In this study, we implemented the NA-MD method, which treats ISC and IC on an equal footing, where the electronic structure is treated at the level of the time-dependent (TD) density-functional tight-binding (DFTB) method, a low-cost semiempirical analog of TD density functional theory (DFT). In particular, the spin-orbit coupling calculation algorithm was implemented in the TD-DFTB framework, and the results showed trends similar to those obtained using TD-DFT. In addition, the NA-MD method successfully reproduced ultrafast ISC of 2-nitronaphthalene.

Unraveling the Photodissociation Branching and Pathways of Methane at 118 nm by Imaging the CH3, CH2, and CH Fragments.

Under irradiation of a vacuum ultraviolet (VUV) photon, methane dissociates and yields multiple fragments. This photochemical behavior is not only of fundamental importance but also with wide-ranging implications in several branches of science. Despite that and numerous previous investigations, the product channel branching is still under debate, and the underlying dissociation mechanisms remain elusive. In this study, the photofragment imaging technique was exploited for the first time to map out the momentum and anisotropy parameter distributions of the CH3, CH2, and CH fragments at the 118 nm photolysis wavelength (10.48 eV photon energy). In conjunction with previously reported results of the H atom fragment at 121.6 nm (10.2 eV), a complete set of product channel branching in both two-body and three-body fragmentations is accurately determined. We concluded that extensive nonadiabatic transitions partake in the processes with two-body fragmentations accounting for more than 90% of overall photodissociation, for which the channel branching values for CH2 + H2 and CH3 + H are about 0.66 and 0.25, respectively. Careful kinematic analysis enables us to untangle the intertwined triple fragmentations into the CH2(X̃ 3B1 and ã 1A1) + H + H and CH(X2Π) + H + H2 channels and to evidence their underlying sequential (or stepwise) mechanisms. With the aid of electronic correlation and prior theoretical calculations of the potential energy surfaces, the most probable or dominant dissociation pathways are elucidated. Comparisons with fragmentary reports in the literature on various photochemical aspects are also documented, and discrepancies are clarified. This comprehensive study benchmarks the VUV photochemistry of methane and advances our understanding of this important process.

Ultrafast x-ray scattering and electronic coherence at avoided crossings: complete isotropic signals

Nonadiabatic transitions at conical intersections and avoided crossings play a pivotal role in shaping the outcomes of photochemical reactions. Using the photodissociation of LiF as a model, this theoretical study explores the application of gas phase nonresonant ultrafast x-ray scattering to map nonadiabatic transitions at an avoided crossing, utilizing the part of the scattering signal that probes electronic coherence directly. The presented scattering signals are rotationally averaged and calculated from two- rather than one-electron (transition) densities, which inherently accounts for all possible electronic transitions driven by the x-ray photon. This approach provides quantitative predictions of the experimental signals, thereby facilitating future experimental endeavors to observe nonadiabatic effects and coherent electron dynamics with ultrafast x-ray scattering.

Dynamical encircling of multiple exceptional points in anti-PT symmetry system

Exceptional points (EPs) in non-Hermitian systems have turned out to be at the origin of many intriguing effects with no counterparts in Hermitian cases. A typically interesting behavior is the chiral mode switching by dynamically winding the EP. Most encircling protocols focus on the two-state or parity-time (PT) symmetry systems. Here, we propose and investigate the dynamical encircling of multiple EPs in an anti-PT-symmetric system, which is constructed based on a one-dimensional lattice with staggered lossy modulation. We reveal that dynamically encircling the multiple EPs results in the chiral dynamics via multiple non-Hermiticity-induced nonadiabatic transitions, where the output state is always on the lowest-loss energy sheet. Compared with the PT-symmetric systems that require complicated variation of the gain/loss rate or on-site potentials, our system only requires modulations of the couplings which can be readily realized in various experimental platforms. Our scheme provides a route to study non-Hermitian physics by engineering the EPs and implement novel photonic devices with unconventional functions.

Manifestation of molecular vibrations of polymers in thermoluminescence of nanocomposites

An experimental and theoretical study of the thermoluminescence (TL) of a PDHS/MCM-41 nanocomposite with the introduction of a polymer (poly-di-n-hexylsilane) (PDHS) into MCM nanopores has been carried out in the temperature range 5–150K. TL curve consists of a very narrow intense band and wider less intense band. In the nananocomposite there is a strong shift of the curve toward low temperatures compared to the curve of the film and a significant narrowing of the bands. The calculations used the model of non-adiabatic transitions. Results show a significant role of molecular vibrations in the formation of the TL curve of a nanocomposite.

Topological Photonic Chiral Mode Converters

AbstractTopological photonic states are immune to structural defects and perturbations, which are considered as a promising solution for realizing robust integrated optical devices. As an essential photonic component, the chiral mode converter, which can directionally switch the modes of photonic states, plays a key role in integrated photonics. However, there is no way to realize topological photonic chiral mode converters. Here, a method is proposed to realize topological photonic chiral mode converters by dynamically encircling exceptional points in topological photonic systems. The device can directionally switch modes of topological photonic states and endow the mode converter with topology protection. Chiral dynamic behavior emerges between the two topological states due to the nonadiabatic transitions within the non‐Hermitian topological photonic system. The topological photonic chiral mode converter is robust against random perturbations of coupling strengths. The realization of a topological chiral mode converter endows topology protection into traditional photonic devices and will promote the practical applications of topological photonic states, such as mode multiplexers and optical isolators.

Virtual mitigation of coherent non-adiabatic transitions by echo verification

Transitions out of the ground space limit the performance of quantum adiabatic algorithms, while hardware imperfections impose stringent limitations on the circuit depth. We propose an adiabatic echo verification protocol which mitigates both coherent and incoherent errors, arising from non-adiabatic transitions and hardware noise, respectively. Quasi-adiabatically evolving forward and backward allows for an echo-verified measurement of any observable. In addition to mitigating hardware noise, our method uses positive-time dynamics only. Crucially, the estimator bias of the observable is reduced when compared to standard adiabatic preparation, achieving up to a quadratic improvement.

Prediction through quantum dynamics simulations: Photo-excited cyclobutanone.

Quantum dynamics simulations are becoming a standard tool for simulating photo-excited molecular systems involving a manifold of coupled states, known as non-adiabatic dynamics. While these simulations have had many successes in explaining experiments and giving details of non-adiabatic transitions, the question remains as to their predictive power. In this work, we present a set of quantum dynamics simulations on cyclobutanone using both grid-based multi-configuration time-dependent Hartree and direct dynamics variational multi-configuration Gaussian methods. The former used a parameterized vibronic coupling model Hamiltonian, and the latter generated the potential energy surfaces on the fly. The results give a picture of the non-adiabatic behavior of this molecule and were used to calculate the signal from a gas-phase ultrafast electron diffraction (GUED) experiment. Corresponding experimental results will be obtained and presented at a later stage for comparison to test the predictive power of the methods. The results show that over the first 500fs after photo-excitation to the S2 state, cyclobutanone relaxes quickly to the S1 state, but only a small population relaxes further to the S0 state. No significant transfer of population to the triplet manifold is found. It is predicted that the GUED experiments over this time scale will see signals related mostly to the C-O stretch motion and elongation of the molecular ring along the C-C-O axis.

Virtual Photon-Mediated Quantum State Transfer and Remote Entanglement between Spin Qubits in Quantum Dots Using Superadiabatic Pulses.

Spin qubits in semiconductor quantum dots are an attractive candidate for scalable quantum information processing. Reliable quantum state transfer and entanglement between spatially separated spin qubits is a highly desirable but challenging goal. Here, we propose a fast and high-fidelity quantum state transfer scheme for two spin qubits mediated by virtual microwave photons. Our general strategy involves using a superadiabatic pulse to eliminate non-adiabatic transitions, without the need for increased control complexity. We show that arbitrary quantum state transfer can be achieved with a fidelity of 95.1% within a 60 ns short time under realistic parameter conditions. We also demonstrate the robustness of this scheme to experimental imperfections and environmental noises. Furthermore, this scheme can be directly applied to the generation of a remote Bell entangled state with a fidelity as high as 97.6%. These results pave the way for fault-tolerant quantum computation on spin quantum network architecture platforms.