Coordinate Path Research Articles

"On-the-Fly" Nonadiabatic Dynamics Simulation on the Ultrafast Photoisomerization of a Molecular Photoswitch Iminothioindoxyl: An RMS-CASPT2 Investigation.

Iminothioindoxyl (ITI) is a new class of photoswitch that exhibits many excellent properties including well-separated absorption bands in the visible region for both conformers, ultrafast Z to E photoisomerization as well as the millisecond reisomerization at room temperature for the E isomer, and switchable ability in both solids and various solvents. However, the underlying ultrafast photoisomerization mechanism at the atomic level remains unclear. In this work, we have employed a combination of high-level RMS-CASPT2-based static electronic structure calculations and nonadiabatic dynamics simulations to investigate the ultrafast photoisomerization dynamics of ITI. Based on the minimum-energy structures, minimum-energy conical intersections, linear interpolation internal coordinate paths, and nonadiabatic dynamics simulations, the overall photoisomerization scenario of ITI upon excitation is established. Upon excitation around 416 nm, the molecule will be excited to the S2 state considering its close energy to the experimentally measured absorption maximum and larger oscillator strength, from which ultrafast decay of S2 to S1 state can take place efficiently with a time constant of 62 fs. However, the photoisomerization is not likely to complete in the S2 state since the dihedral associated with the Z to E isomerization changes little during the relaxation. Upon relaxing to the S1 state, the molecule will decay to the S0 state ultrafast with a time constant of 232 fs. In contrast, the decay of the S1 state is important for the isomerization considering that the dihedral related to the isomerization of the hopping structures is close to 90°. Therefore, the S1/S0 intersection region should be important for the isomerization of ITI. Arriving at the S0 state, the molecule can either go back to the original Z reactant or isomerize to the E products. At the end of the 500 fs simulation time, the E configuration accounts for nearly 37% of the final structures. Moreover, the photoisomerization mechanism is different from the isomerization mechanism in the ground state; i.e., instead of the inversion mechanism in the ground state, the photoisomerization prefers the rotation mechanism. Our results not only agree well with previous experimental studies but also provide some novel insights that could be helpful for future improvements in the performance of the ITI photoswitches.

VSCF/VCI theory based on the Podolsky Hamiltonian.

While the vibrational spectra of semi-rigid molecules can be computed on approaches relying on the Watson Hamiltonian, floppy molecules or molecular clusters are better described by Hamiltonians, which are capable of dealing with any curvilinear coordinates. It is the kinetic energy operator (KEO) of these Hamiltonians, which render the correlated calculations relying on them rather costly. Novel implementation of vibrational self-consistent field theory and vibrational configuration interaction theory on the basis of the Podolsky Hamiltonian are reported, in which the inverse of the metric tensor, i.e., the G matrix, is represented by an n-mode expansion expressed in terms of polynomials. An analysis of the importance of the individual terms of the KEO with respect to the truncation orders of the n-mode expansion is provided. Benchmark calculations have been performed for the cis-HOPO and methanimine, H2CNH, molecules and are compared to experimental data and to calculations based on the Watson Hamiltonian and the internal coordinate path Hamiltonian.

Influence of atomic electronegativity on ESIPT behaviour for the BTDI and its derivatives: Theoretical exploration

In this work, we theoretically explored the influence of atomic electronegativity on excited-state intramolecular proton transfer (ESIPT) behavior among novel fluorescent probes BTDI and its derivatives (BODI and BSeDI). A thorough examination of the optimized structural parameters and infrared vibrational spectra reveals an enhancement in intramolecular hydrogen bonding within BTDI and its derivatives upon light excitation. This finding is further reinforced by topological analysis and interaction region indicator scatter plots, which underscores the sensitivity of atomic electronegativity to variations in hydrogen bonding strength. With regards to absorption and fluorescence spectra, the decrease in atomic electronegativity leads to a pronounced redshift, primarily attributed to the narrowing of the energy gap. Additionally, an analysis of potential energy curves and the exploration of intrinsic reaction coordinate paths based on transition state structures afford a deeper understanding of the mechanism underlying ESIPT and being modulated through the manipulation of atomic electronegativity. We anticipate that this work on atomic electronegativity regulating ESIPT behavior will serve as a catalyst for novel fluorescent probes in the future, offering fresh perspectives and insights.

Exploring Downhill Bifurcations in [3,3]-Sigmatropic Rearrangement by Finding Transitions from an Uphill Bifurcation to a Downhill Bifurcation.

Downhill bifurcation is a phenomenon in which an ensemble of trajectories passing through a transition state (TS), called an ambimodal TS, bifurcates into multiple products. Finding downhill bifurcations for unreported pairs of chemical transformations is essential, because they affect reaction selectivity. Marx et al. reported that perturbations such as applying mechanical stress or changing a substituent cause a transition from an uphill bifurcation to a downhill bifurcation in the ring-opening reaction of cyclopropane derivatives (ChemPhysChem, 2018, 19, 837-847). Investigating the occurrence of this phenomenon in other reactions, especially in pericyclic reactions, is interesting for understanding and controlling the reaction selectivity considering downhill bifurcations. In this study, we proposed a method for finding perturbation-induced downhill bifurcations and applied it to three pericyclic reactions. The transition from an uphill bifurcation to a downhill bifurcation occurred in two of the three pericyclic reactions, one of which was previously unreported. Interestingly, the occurrence of a downhill bifurcation by a perturbation depended on the directions of the intrinsic reaction coordinate paths of the two TSs when they emerged from the reactant minimum. Our method can be applied in mechanistic studies to avoid the risk of overlooking downhill bifurcations.

UAV search coverage under priority of important targets based on multi-location domain decomposition

<abstract> <p>In recent years, the coverage path planning (CPP) of unmanned aerial vehicles (UAVs) has attracted attention in reconnaissance, patrol, and search and rescue efforts, aiming to plan the paths for UAVs to cover a specified area as efficiently as possible. This paper proposes a UAV path fast coverage model to prioritize important targets with domain composition based on the starting point and location of the targets, combined with the domain decomposition strategy of important targets. Considering the constraints of the number of UAVs, the number of operators, and the flight time, the parallel search strategy can plan the coverage scheme with the shortest search time for the search range, and further obtain the coordinate points and path coordinates of the UAV turning. Finally, through multiple simulation experiments in four maps of various islands, the proposed method is verified to have an improved performance compare to the two track path coverage algorithms methods in terms of the coverage efficiency and the time complexity, thus providing a more scientific basis for the path coverage research of multi-target searches.</p> </abstract>

ОСОБЛИВОСТІ ПЛАНУВАННЯ КООРДИНАТ ТРАЄКТОРНИХ ТОЧОК АВТОНОМНОГО СУДНА З УРАХУВАННЯМ НАВІГАЦІЙНИХ РИЗИКІВ

Marine autonomous surface vessels came both numerous advantages and critical dangers that must be addressed early. The accident rate of autonomous vessels during the voyage cycle has an elevated level of navigational risk and the impact of cyberattacks due to the large number of receivers and transmitters of the maneuvering parameter control system and motion control coordinates along the planned trajectory. To organize accident-free navigation, it is necessary to perform highprecision planning of path coordinates using the method of trajectory points (TP), which takes into account the geometry of the path and the characteristics of the vessel. After this, it is necessary to identify hazardous areas by engineering means, determine the type of navigational risks, and plan ways to manage their level, to prepare shore operators and automatic ship control systems for maneuvering under the conditions of risks that may occur during its use. The solution to this problem should begin with the compilation of a generalized table of navigational risks and their percentage probability, and methods that will help avoid risks. One of the modern methods of determining risks is the engineering method of managing navigational risks, which determines the frequency of occurrence of various kind of risks and allows to provide preventive methods for the safe use of autonomous vessels by managing of their level. The methods of determining main navigational risks were proposed in this research, as well as systems of planning them in order to ensure the proper control. The obtained results can be used to ensure the navigational safety of autonomous vessels and also to improve methods of navigational risks planning and management by their level in the context of autonomous vessels application. Keywords: navigation risks, engineering method, safety planning of the trajectory points, managing by the safety level of autonomous ships.

Time-Optimal Path Tracking for Dual-Arm Free-Floating Space Manipulator System Using Convex Programming

In this paper, the time-optimal path tracking problem of the dual-arm free-floating space manipulator (FFSM) system is solved by using convex programming. Firstly, we construct a continuous nonlinear optimization problem that considers system dynamics and constraints along the path, including torque, velocity and acceleration. Subsequently, the original optimization problem is transformed into a convex optimal control problem by using scalar path coordinate and nonlinear variables. To characterize the problem in a more manageable form, we apply the direct transcription method and discretize the problem into a sparse convex optimization program. Numerical results demonstrate that the proposed approach efficiently determines the trajectory of the FFSM along the preset path. Meanwhile, the base's velocity can be limited to a small region, which is an essential requirement for ensuring the stability of the satellite. Furthermore, an experiment is conducted using GLUON robots. The tracking error between the actual and preset pose of the target verifies the feasibility of the proposed method.

The increased Diels–Alder reactivity of umpolung tropone: analysis of individual atoms and bonds using QTAIM and IQA along complete IRC paths

AbstractA fruitful debate took place recently in literature, discussing the enhanced Diels–Alder reactivity of tropone derivatives for which the carbonyl polarity was reversed by means of umpolung. Karas et al. sustained that the umpolung increases the antiaromatic character of the ring, affecting the highest occupied molecular orbital (HOMO)/least unoccupied molecular orbital (LUMO) energies, speeding up the reaction. Tiekink et al. challenged this interpretation by sustaining that the asynchronicity of the reaction mechanisms, rather than orbital energy perturbation, was the main responsible for the smaller reaction barriers. We shed light on this dispute by computing full interaction quantum atom (IQA) and quantum theory of atoms in molecules (QTAIM) analyses over complete intrinsic reaction coordinate (IRC) paths for the Diels–Alder reaction of tropone and its umpolung derivatives, using the same systems studied by Karas et al. and Tiekink et al. Our results confirm that the asynchronicity is indeed very high for those reactions with smaller reaction barriers and offer an atom‐by‐atom and bond‐by‐bond analysis of the entire IRC pathways. Even though asynchronicity and lower reactions barriers seem to be related, antiaromaticity and lower barriers are related as well, but discussing both these interpretations does not necessarily require arguments on HOMO/LUMO energies to be invoked.

3D Information-Theoretic Analysis of the Simplest Hydrogen Abstraction Reaction.

We investigate the course of an elementary chemical reaction from the perspective of information theory in 3D space through the hypersurface of several information-theoretic (IT) functionals such as disequilibrium (D), Shannon entropy (S), Fisher information (I), and the complexity measures of Fisher-Shannon (FS) and López-Mancini-Calbet (LMC). The probe for the study is the hydrogenic identity abstraction reaction. In order to perform the analysis, the reactivity pattern of the reaction is examined by use of the aforementioned functionals of the single-particle density, which is analyzed in position (r) and momentum (p) spaces. The 3D analyses revealed interesting reactivity patterns in the neighborhood of the intrinsic reaction coordinate (IRC) path, which allow to interpret the reaction mechanism for this reaction in a novel manner. In addition, the chemically interesting regions that have been characterized through the information functionals and their complexity measures are depicted and analyzed in the framework of the three-dimensional structure of the information-theoretical data of a chemical reaction, that is, the reactant/product (R/P) complexes, the transition state (TS), and the ones that are only revealed through IT measures such as the bond-cleavage energy region (BCER), the bond-breaking/forming (B-B/F) region, and the spin-coupling (SC) process. Furthermore, focus has been placed on the diagonal part of the hypersurface of the IT functionals, aside from the IRC path itself, with the purpose of analyzing the dissociation process of the triatomic transition-state complex that has revealed other interesting features of the bond-breaking (B-B) process. In other respects, it is shown throughout the combined analyses of the 3D structure of the IT functionals in conjugated spaces that the chemically significant regions occurring at the onset of the TS are completely characterized by information-theoretic aspects of localizability (S), uniformity (D), and disorder. Further, novel regions of low complexity seem to indicate new boundaries for chemically stable complex molecules. Finally, the study reveals that the chemical reaction occurs at low-complexity regions, where the concurrent phenomena take place: bond-breaking/forming (B-B/F), bond-cleavage energy reservoirs (BCER), spin-coupling (SC), and transition state (TS).

Ortho-para interconversion of nuclear states of H2O through replica transition state: prospect of quantum entanglement at homodromic Bjerrum defect site

ContextFrom a nuclear spin prospective, water exists as para and ortho nuclear spin isomers (isotopomers). Spin interconversions in isolated molecules of water are forbidden, but many recent reports have shown them to happen in bulk, through dynamic proton exchanges happening between interconnected networks of a large array of water molecules. In this contribution, a possible explanation for an unexpected slow or delayed interconversion of ortho-para water in ice observed in an earlier reported experiment is provided. Using the results of quantum mechanical investigations, we have discussed the roles played by Bjerrum defects in the dynamic proton exchanges and ortho-para spin state interconversions. We guess that at the sites of the Bjerrum defects, there are possibilities of quantum entanglements of states, through pairwise interactions. Based on the perfectly correlated exchange happening via a replica transition state, we speculate that it can have significant influences on ortho-para interconversions of water. We also conjecture that the overall ortho-para interconversion is not a continuous process, rather can be imagined to be happening serendipitously, but within the boundary of the rules of quantum mechanics.MethodsAll computations were performed with Gaussian 09 program. B3LYP/6-31++G(d,p) methodology was used to compute all the stationary points. Further energy corrections were computed using CCSD(T)/aug-cc-pVTZ methodology. Intrinsic reaction coordinate (IRC) path computations were carried out for the transition states.

Theoretical Investigation of the E/Z Photoisomerization Pathway in 1-(2-Pyrrolyl)-2-(2-thienyl)ethylene.

Molecular-level understanding of photochemistry in simple vinylene-linked systems such as ethylene and stilbene has been a major area of research. However, the effect of replacing the two benzene rings by five-membered heterocyclic rings, thiophene and pyrrole, is yet to be reported. In the present theoretical study, our aim is to illustrate photoinduced processes in a vinylene-linked thiophene-pyrrole system. Computational studies are carried out at the RI-MP2/RI-ADC(2)/cc-pVTZ level to explore different isomerization pathways. Minimum-energy conical intersection (MECI) structures are categorized into two types: closed-ring and twisted-pyramidalized structures. Relaxation through the former MECIs is accessible only from the cis isomers. However, the latter MECIs are inaccessible due to high energy barriers along the linear interpolation in internal coordinate paths.

The importance of nuclear dynamics in reaction mechanisms of acetylene cyclotrimerization catalyzed by Fe+-compounds

The reaction mechanism of transition metal-catalyzed [2 + 2 + 2] cyclotrimerization of three acetylenes to form benzene consists of multiple steps, including the generation of a metallacyclopentadiene intermediate through the coupling of two acetylenes and subsequent [4 + 2] cycloaddition. Using quantum chemical calculations, we show that acetylene cyclotrimerization catalyzed by Fe+–L-type compounds (where L represents the ligands F−, Cl−, OH−, SH−, NC−, NH3, H2O, and cyclopentadienyl anion) can occur via a concerted single-step mechanism, where the reactant complex (C2H2)3–Fe+–L is directly connected to the C6H6–Fe+–L product complex via a single intrinsic reaction coordinate (IRC) path with one transition state. We then performed trajectory calculations, starting from concerted transition state structures with small kinetic energies, to confirm the efficient formation of benzene via this single-step mechanism. Interestingly, we found that many of the trajectories exhibited non-IRC dynamics—the trajectories did not directly lead to the formation of the benzene product, but to that of the C2H2–Fe+–L–C4H4 intermediate; in contrast, direct benzene formation predominantly occurred for the compounds comprising the ligands F− and NC−. Thus, we report that nuclear dynamics play an important role in determining the cyclotrimerization reaction mechanism, and that the properties of the potential energy surface depend on the ligand molecule.

Optimal smooth polynomial lane change generation for autonomous racing

Online path re-planning is a crucial task for the control of autonomous vehicles, especially when driving at the handling limits in a dynamic environment. In this article, we propose a fast path planning algorithm meant for trajectory change scenarios, that is tailored to generate smooth reference paths. The proposed solution is based on a convex combination of the current and target paths, and guarantees heading and curvature continuity. Additionally, we complete the algorithm with a real-time compliant nonlinear program to generate nearly-time-optimal maneuvers. The proposed approach is tested on a driving simulator and compared against state-of-the-art solutions, which typically rely on numerical differentiation of path coordinates, often introducing inaccuracy and yielding inefficient or imprecise solutions.

EEMD-based videogrammetry and vibration analysis method for rotating wind power blades

It is difficult to measure the dynamic status because of the far fields working environment of the wind turbine. A method for vibration analysis of wind turbine blades based on videogrammetry is proposed. In order to obtain the space arc-like path coordinates of rotating blades, a videogrammetry experimental platform for rotating wind power blades was constructed. The space arc-like blade measuring points are collected and the error analysis is carried out by fitting the circular arc-like paths. The natural frequency of blade vibration is calculated based on Ensemble Empirical Mode Decomposition (EEMD) and fast Fourier transform (FFT). Evaluate the accuracy of the proposed method through finite element analysis (FEA) and hammering experiment. The results show that the modal & frequency from the presented method are basically consistent with the results of FEA and hammering experiment. It provides a theoretical method and technical means for measuring the dynamic vibration characteristics of blades.

Strategies to Enhance the Rate of Proton‐Coupled Electron Transfer Reactions in Dye‐Water Oxidation Catalyst Complexes

AbstractA thorough understanding of the proton‐coupled electron transfer (PCET) steps that are involved in photocatalytic water oxidation is of crucial importance in order to increase the efficiency of dye‐sensitized photoelectrochemical cells (DS‐PEC) for solar to fuel conversion. This work provides a computational investigation of the ground and excited state potential energy surfaces of PCET reactions in two supramolecular dye‐catalyst complexes for photocatalytic water splitting. The intrinsic reaction coordinate path is computed for the rate limiting PCET step in the catalytic cycle for both complexes. By using time‐dependent density functional theory calculations, we show that the ground and excited state potential energy surfaces have a (near) degeneracy in the region of the PCET transition state. We discuss two possible strategies that take advantage of this feature to accelerate the PCET reaction: (i) through optimizing the conditions for vibronic coupling by chemical design and synthesis or (ii) through populating the product state with appropriately tuned laser pulses.

Unraveling photo-induced proton transfer mechanism and proposing solvent regulation manner for the two intramolecular proton-transfer-site BH-BA fluorophore

To expound specific excited state processes of the novel excitation wavelength dependent emission BH-BA fluorophore for better subsequent applications, this wok mainly focus on exploring photo-induced hydrogen bonding geometrical changes, excited state intramolecular proton transfer (ESIPT) mechanism and related regulated behavior via solvent polarity. The differences of structural parameters, infrared (IR) vibrational spectra, core-valence bifurcation (CVB) index as well as electronic densities ρ(r) between S0 and S1 states related to dual hydrogen bonds (O1-H2···N3 and O4-H5···N6) reveal S1-state hydrogen bonding strength facilitate ESIPT behaviors for BH-BA system. Of particular note, O4-H5···N6 plays a more dominant role. Photo-induced intramolecular charge transfer (ICT) and variations of Hirshfled and NPA charges over atoms related to hydrogen bonding moieties promote the ESIPT tendency for BH-BA. Combined potential energy surfaces (PESs), transition state (TS) and intrinsic reaction coordinate (IRC) paths, we illustrate the excited state intramolecular single proton transfer (ESISPT) mechanism of BH-BA should occur along with O4-H5···N6 hydrogen bonding wire, which could be adjusted by surrounding solvent polarity.

IMU Aided GPS Based Navigation of Ackermann Steered Rover

GPS signal loss is a major issue when the navigation system of rovers is based solely on GPS for outdoor navigation rendering the rover stuck in the mid of the road in case of signal loss. In this study, a low-cost IMU aided GPS-based navigation system for Ackermann Steered mobile robots is presented and tested to cater to the issue of GPS signal loss along. GPS path is selected and fed using the android application which provides real-time location tracking of the rover on the map embedded into the application. System utilizes Arduino along with the node MCU, compass, IMU, Rotary encoders, and an Ackermann steered rover. Controller processes the path file, compares its current position with the path coordinates and navigates using inertial sensor aided navigation algorithm, avoiding obstacles to reach its destination. IMU measures the distance traveled from each path point, and in case of signal loss, it makes the rover move for the remaining distance in the direction of destination point. Rover faced a sinusoidal motion due to the steering, so PID was implemented. The system was successfully tested on the IST premises and finds its application in the delivery trolley, institutional delivery carts, and related applications.

Excited-state double proton transfer of 1,8-dihydroxy-2-naphthaldehyde: A MS-CASPT2//CASSCF study

Excited-state double proton transfer (ESDPT) is a controversial issue which has long been plagued with theoretical and experimental communities. Herein, we took 1,8-dihydroxy-2-naphthaldehyde (DHNA) as a prototype and used combined complete active space self-consistent field (CASSCF) and multi-state complete active-space second-order perturbation (MS-CASPT2) methods to investigate ES-DPT and excited-state deactivation pathways of DHNA. Three different tautomer minima of S1-ENOL, S1-KETO-1, and S1-KETO-2 and two crucial conical intersections of S1S0-KETO-1 and S1S0-KETO-2 in.and between the S0 and S1 states were obtained. S1-KETO-1 and S1-KETO-2 should take responsibility for experimentally observing dual-emission bands. In addition, two-dimensional potential energy surfaces (2D-PESs) and linear interpolated internal coordinate paths connecting relevant structures were calculated at the MS-CASPT2//CASSCF level and confirmed a stepwise ESDPT mechanism. Specifically, the first proton transfer from S1-ENOL to S1-KETO-1 is barrierless, whereas the second one from S1-KETO-1 to S1-KETO-2 demands a barrier of ca. 6.0 kcal/mol. The linear interpolated internal coordinate path connecting S1-KETO-1 (S1-KETO-2) and S1S0-KETO-1 (S1S0-KETO-2) is uphill with a barrier of ca. 12.0 kcal/mol, which will trap DHNA in the S1 state while therefore enabling dual-emission bands. On the other hand, the S1/S0 conical intersections would also prompt the S1 system to decay to the S0 state, which could be to certain extent suppressed by locking the rotation of the C5−C8−C9−O10 dihedral angle. These mechanistic insights are not only helpful for understanding ESDPT but also useful for designing novel molecular materials with excellent photoluminescent performances.

Smooth and proximate time-optimal trajectory planning of robotic manipulators

The simultaneous achievement of high accuracy and productivity in robotics has been extensively investigated using the trajectory planning approach. We propose a smooth and proximate time-optimal trajectory planning method. First, we generated the velocity limit curve by expressing joint torque and joint velocity constraints as a function of the path coordinate. Then, we calculated the time-optimal trajectory using a dynamic programming technique and fitted the smooth cubic spline. The smoothing factor of the cubic spline curve was optimized by applying a binary recursive. The proposed method can guarantee the continuity and smoothness of joint torque. The simulation results showed that the proposed method can reduce joint-jerk and improve the tracking accuracy of the controller.

Path-Integral Monte Carlo Worm Algorithm for Bose Systems with Periodic Boundary Conditions

We provide a detailed description of the path-integral Monte Carlo worm algorithm used to exactly calculate the thermodynamics of Bose systems in the canonical ensemble. The algorithm is fully consistent with periodic boundary conditions, which are applied to simulate homogeneous phases of bulk systems, and it does not require any limitation in the length of the Monte Carlo moves realizing the sampling of the probability distribution function in the space of path configurations. The result is achieved by adopting a representation of the path coordinates where only the initial point of each path is inside the simulation box, the remaining ones being free to span the entire space. Detailed balance can thereby be ensured for any update of the path configurations without the ambiguity of the selection of the periodic image of the particles involved. We benchmark the algorithm using the non-interacting Bose gas model for which exact results for the partition function at finite number of particles can be derived. Convergence issues and the approach to the thermodynamic limit are also addressed for interacting systems of hard spheres in the regime of high density.