Hopping Algorithm Research Articles

Landau-Zener type surface hopping algorithms.

A class of surface hopping algorithms is studied comparing two recent Landau-Zener (LZ) formulas for the probability of nonadiabatic transitions. One of the formulas requires a diabatic representation of the potential matrix while the other one depends only on the adiabatic potential energy surfaces. For each classical trajectory, the nonadiabatic transitions take place only when the surface gap attains a local minimum. Numerical experiments are performed with deterministically branching trajectories and with probabilistic surface hopping. The deterministic and the probabilistic approach confirm the affinity of both the LZ probabilities, as well as the good approximation of the reference solution computed by solving the Schrödinger equation via a grid based pseudo-spectral method. Visualizations of position expectations and superimposed surface hopping trajectories with reference position densities illustrate the effective dynamics of the investigated algorithms.

Estimating the entropy and quantifying the impurity of a swarm of surface-hopping trajectories: a new perspective on decoherence.

In this article, we consider the intrinsic entropy of Tully's fewest switches surface hopping (FSSH) algorithm (as estimated by the impurity of the density matrix) [J. Chem. Phys. 93, 1061 (1990)]. We show that, even for a closed system, the total impurity of a FSSH calculation increases in time (rather than stays constant). This apparent failure of the FSSH algorithm can be traced back to an incorrect, approximate treatment of the electronic coherence between wavepackets moving along different potential energy surfaces. This incorrect treatment of electronic coherence also prevents the FSSH algorithm from correctly describing wavepacket recoherences (which is a well established limitation of the FSSH method). Nevertheless, despite these limitations, the FSSH algorithm often predicts accurate observables because the electronic coherence density is modulated by a phase factor which varies rapidly in phase space and which often integrates to almost zero. Adding "decoherence" events on top of a FSSH calculation completely destroys the incorrect FSSH electronic coherence and effectively sets the Poincaré recurrence time for wavepacket recoherence to infinity; this modification usually increases FSSH accuracy (assuming there are no recoherences) while also offering long-time stability for trajectories. In practice, we show that introducing "decoherence" events does not change the total FSSH impurity significantly, but does lead to more accurate evaluations of the impurity of the electronic subsystem.

Muse: Multi-algorithm collaborative crystal structure prediction

The algorithm and testing of the Multi-algorithm-collaborative Universal Structure-prediction Environment (Muse) are detailed. Presently, in Muse I combined the evolutionary, the simulated annealing, and the basin hopping algorithms to realize high-efficiency structure predictions of materials under certain conditions. Muse is kept open and other algorithms can be added in future. I introduced two new operators, slip and twist, to increase the diversity of structures. In order to realize the self-adaptive evolution of structures, I also introduced the competition scheme among the ten variation operators, as is proved to further increase the diversity of structures. The symmetry constraints in the first generation, the multi-algorithm collaboration, the ten variation operators, and the self-adaptive scheme are all key to enhancing the performance of Muse. To study the search ability of Muse, I performed extensive tests on different systems, including the metallic, covalent, and ionic systems. All these present tests show that Muse has very high efficiency and 100% success rate.

Nonadiabatic Excited-State Molecular Dynamics: Modeling Photophysics in Organic Conjugated Materials

To design functional photoactive materials for a variety of technological applications, researchers need to understand their electronic properties in detail and have ways to control their photoinduced pathways. When excited by photons of light, organic conjugated materials (OCMs) show dynamics that are often characterized by large nonadiabatic (NA) couplings between multiple excited states through a breakdown of the Born-Oppenheimer (BO) approximation. Following photoexcitation, various nonradiative intraband relaxation pathways can lead to a number of complex processes. Therefore, computational simulation of nonadiabatic molecular dynamics is an indispensable tool for understanding complex photoinduced processes such as internal conversion, energy transfer, charge separation, and spatial localization of excitons. Over the years, we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework that efficiently and accurately describes photoinduced phenomena in extended conjugated molecular systems. We use the fewest-switches surface hopping (FSSH) algorithm to treat quantum transitions among multiple adiabatic excited state potential energy surfaces (PESs). Extended molecular systems often contain hundreds of atoms and involve large densities of excited states that participate in the photoinduced dynamics. We can achieve an accurate description of the multiple excited states using the configuration interaction single (CIS) formalism with a semiempirical model Hamiltonian. Analytical techniques allow the trajectory to be propagated "on the fly" using the complete set of NA coupling terms and remove computational bottlenecks in the evaluation of excited-state gradients and NA couplings. Furthermore, the use of state-specific gradients for propagation of nuclei on the native excited-state PES eliminates the need for simplifications such as the classical path approximation (CPA), which only uses ground-state gradients. Thus, the NA-ESMD methodology offers a computationally tractable route for simulating hundreds of atoms on ~10 ps time scales where multiple coupled excited states are involved. In this Account, we review recent developments in the NA-ESMD modeling of photoinduced dynamics in extended conjugated molecules involving multiple coupled electronic states. We have successfully applied the outlined NA-ESMD framework to study ultrafast conformational planarization in polyfluorenes where the rate of torsional relaxation can be controlled based on the initial excitation. With the addition of the state reassignment algorithm to identify instances of unavoided crossings between noninteracting PESs, NA-ESMD can now be used to study systems in which these so-called trivial unavoided crossings are expected to predominate. We employ this technique to analyze the energy transfer between poly(phenylene vinylene) (PPV) segments where conformational fluctuations give rise to numerous instances of unavoided crossings leading to multiple pathways and complex energy transfer dynamics that cannot be described using a simple Förster model. In addition, we have investigated the mechanism of ultrafast unidirectional energy transfer in dendrimers composed of poly(phenylene ethynylene) (PPE) chromophores and have demonstrated that differential nuclear motion favors downhill energy transfer in dendrimers. The use of native excited-state gradients allows us to observe this feature.

The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: a combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface.

We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam-surface scattering is combined with vibrational overtone pumping and quantum-state selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions.

An adaptive range-free localisation protocol in wireless sensor networks

It is well known that localisation is a fundamental issue for many wireless network applications. Without the need of additional ranging devices, the range–free localisation technology is a cost–effective solution for low–cost indoor and outdoor wireless sensor networks. However, we noted that most existing algorithms were only studied using tools like MATLAB neglecting possible problems in a real wireless network context such as frame collision and node synchronisation. Thus, we propose an adaptive range–free localisation protocol (ALP) based on IEEE 802.15.4 standard, which can evaluate localisation algorithms. Using our localisation protocol, we investigate and compare the performance of our new approach to some existing range–free algorithms in terms of localisation accuracy, mobility, synchronisation and overhead. Our results show that our Mid–perpendicular, Checkout DV–hop and Selective 3–Anchor DV–hop algorithms support robust and dynamic localisation in the context of our adaptive localisation protocol.

3D DV-hop localisation scheme based on particle swarm optimisation in wireless sensor networks

To improve the node localisation performance of the distance vector–hop (DV–hop) algorithm in the three–dimensional (3D) space, an improved range–free node localisation algorithm in the 3D wireless sensor networks is proposed by analysing the lack of the existing 3D localisation algorithms. After performing the 3D DV–hop algorithm, we use the particle swarm optimisation (PSO) algorithm with the inertia weight to emend unknown nodes' location estimated by the 3D DV–hop algorithm. The simulation results show that the proposed algorithm, in comparison with the original 3D DV–hop algorithm, greatly reduces the localisation error and error variance. It enhances the localisation precision and stability effectively without increasing the additional hardware and communication cost.

Can we derive Tully's surface-hopping algorithm from the semiclassical quantum Liouville equation? Almost, but only with decoherence

In this article, we demonstrate that Tully's fewest-switches surface hopping (FSSH) algorithm approximately obeys the mixed quantum-classical Liouville equation (QCLE), provided that several conditions are satisfied--some major conditions, and some minor. The major conditions are: (1) nuclei must be moving quickly with large momenta; (2) there cannot be explicit recoherences or interference effects between nuclear wave packets; (3) force-based decoherence must be added to the FSSH algorithm, and the trajectories can no longer rigorously be independent (though approximations for independent trajectories are possible). We furthermore expect that FSSH (with decoherence) will be most robust when nonadiabatic transitions in an adiabatic basis are dictated primarily by derivative couplings that are presumably localized to crossing regions, rather than by small but pervasive off-diagonal force matrix elements. In the end, our results emphasize the strengths of and possibilities for the FSSH algorithm when decoherence is included, while also demonstrating the limitations of the FSSH algorithm and its inherent inability to follow the QCLE exactly.

Communication: The correct interpretation of surface hopping trajectories: How to calculate electronic properties

In a recent paper, we presented a road map for how Tully's fewest switches surface hopping (FSSH) algorithm can be derived, under certain circumstances, from the mixed quantum-classical Liouville equation. In this communication, we now demonstrate how this new interpretation of surface hopping can yield significantly enhanced results for electronic properties in nonadiabatic calculations. Specifically, we calculate diabatic populations for the spin-boson problem using FSSH trajectories. We show that, for some Hamiltonians, without changing the FSSH algorithm at all but rather simply reinterpreting the ensemble of surface hopping trajectories, we recover excellent results and remove any and all ambiguity about the initial condition problem.

모바일 에드 혹 네트워크에서 노드의 방향성을 고려한 에너지 효율적 라우팅 알고리즘 연구

We proposed the context-awareness routing algorithm DDV (Dynamic Direction Vector)-hop algorithm at Mobile Ad-hoc Network(MANET). MANET has problem about dynamic topology, the lack of scalability of the network by mobile of node. By mobile of node, energy consumption rate is different. So it is important choosing routing algorithms for the minium of energy consumption rate. DDV-hop algorithms considers of the attribute of mobile node, create a cluster and maintain. And it provides a path by searching a route more energy efficient. We apply mobile of node by direction and time, the alogorighm of routning path and energy efficiency clustering is provided, it is shown the result of enery consumption that is optimized for the network.

Quantum Trajectory Approach to Molecular Dynamics Simulation with Surface Hopping

In this work we propose a quantum trajectory approach to the powerful molecular dynamics simulation with surface hopping, from an insight that an effective “observation" is actually implied in the simulation through tracking the forces experienced, just like checking the meter's result in quantum measurement process. This treatment can build the nonadiabatic surface hopping on a physical foundation, instead of the usual fictitious and conceptually inconsistent hopping algorithms. The effects and advantages of the proposed scheme are preliminarily illustrated by a two-surface model system.

A variational surface hopping algorithm for the sub-Ohmic spin-boson model

The Davydov D1 ansatz, which assigns individual bosonic trajectories to each spin state, is an efficient, yet extremely accurate trial state for time-dependent variation of the sub-Ohmic spin-boson model [N. Wu, L. Duan, X. Li, and Y. Zhao, J. Chem. Phys. 138, 084111 (2013)]. A surface hopping algorithm is developed employing the Davydov D1 ansatz to study the spin dynamics with a sub-Ohmic bosonic bath. The algorithm takes into account both coherent and incoherent dynamics of the population evolution in a unified manner, and compared with semiclassical surface hopping algorithms, hopping rates calculated in this work follow more closely the Marcus formula.

A Fast Rendezvous Channel-Hopping Algorithm for Cognitive Radio Networks

Cognitive radio networks (CRNs) have emerged as a critical technique to enhance the utilization of licensed channels. In CRNs, each secondary user (SU) should not interfere the co-locate incumbent networks. For this purpose, before data transmission, SUs should rendezvous on an available channel (i.e., idle and licensed channel) for establishing a link or exchanging control information. However, implementation of rendezvous is challenging since SUs are not aware of the presence of each other before rendezvous and available channels sensed by each SU may be different. In this paper, we proposed a fast rendezvous channel hopping algorithm (FRCH), which can guarantee rendezvous within 2N2 + N timeslots under asynchronous environments, where N denotes the number of licensed channels in a CRN.

Experimental and Theoretical Study of Multi-Quantum Vibrational Excitation: NO(v = 0→1,2,3) in Collisions with Au(111)

We measured absolute probabilities for vibrational excitation of NO(v = 0) molecules in collisions with a Au(111) surface at an incidence energy of translation of 0.4 eV and surface temperatures between 300 and 1100 K. In addition to previously reported excitation to v = 1 and v = 2, we observed excitation to v = 3. The excitation probabilities exhibit an Arrhenius dependence on surface temperature, indicating that the dominant excitation mechanism is nonadiabatic coupling to electron-hole pairs. The experimental data are analyzed in terms of a recently introduced kinetic model, which was extended to include four vibrational states. We describe a subpopulation decomposition of the kinetic model, which allows us to examine vibrational population transfer pathways. The analysis indicates that sequential pathways (v = 0 → 1 → 2 and v = 0 → 1 → 2 → 3) alone cannot adequately describe production of v = 2 or 3. In addition, we performed first-principles molecular dynamics calculations that incorporate electronically nonadiabatic dynamics via an independent electron surface hopping (IESH) algorithm, which requires as input an ab initio potential energy hypersurface (PES) and nonadiabatic coupling matrix elements, both obtained from density functional theory (DFT). While the IESH-based simulations reproduce the v = 1 data well, they slightly underestimate the excitation probabilities for v = 2, and they significantly underestimate those for v = 3. Furthermore, this implementation of IESH appears to overestimate the importance of sequential energy transfer pathways. We make several suggestions concerning ways to improve this IESH-based model.

Cluster Based Energy Routing System for Wireless Sensor Networks

Wireless Sensor Network has become part of everyday life. Due to very small size of sensor nodes and their limited battery power a lot of work has been done in the area of energy management. Many routing protocols have been developed for using battery power efficiently but these protocols sacrifice QoS for this energy efficiency. Energy Harvesting technologies have been proposed to improve the lifetime of sensor nodes. Sensor nodes are charged by using environmental sources such as light, wind, vibration etc. These energy harvesting technologies have been combined with energy transference methods for transference of energy from one node to another. The new area of research is multi hop energy transference and algorithms for energy routing. This research paper is about a cluster based architecture that can help in transporting energy easily and efficiently from one node to another; an algorithm has been designed for charging the nodes before depleting their entire energy. 

An Adaptive Channel Hopping Algorithm for Wireless Sensor Network with Mesh Structure

Abstract According to EGTS proposal, an adaptive channel hopping algorithm that can be used in wireless mesh sensor networks was is designed in this paper. The nodes select proper channels independently and use them to communicate with their neighbors. Once a pair of nodes find their current channel has been deteriorated, they abandoned the current channel and enable the reserved channel, so that the reliability of the network is improved. The algorithm is compatible with the primitives and the frame structure of EGTS and makes use of multi-channels efficiently. The data structure and the procedure of the mechanism were described in detail and the feasibility and the efficiency was given by analysis and experiment. Finally, it is concluded that the algorithm is practicable when the density of network is less than 8 and the topology is relatively static.

HUNTING FOR YOUNG DISPERSING STAR CLUSTERS IN IC 2574

Dissolving stellar groups are very difficult to detect using traditional surface photometry techniques. We have developed a method to find and characterize non-compact stellar systems in galaxies where the young stellar population can be spatially resolved. By carrying out photometry on individual stars, we are able to separate the luminous blue stellar population from the star field background. The locations of these stars are used to identify groups by applying the HOP algorithm, which are then characterized using color-magnitude and stellar density radial profiles to estimate age, size, density, and shape. We test the method on Hubble Space Telescope Advanced Camera for Surveys archival images of IC 2574 and find 75 dispersed stellar groups. Of these, 20 highly dispersed groups are good candidates for dissolving systems. We find few compact systems with evidence of dissolution, potentially indicating that star formation in this galaxy occurs mostly in unbound clusters or groups. These systems indicate that the dispersion rate of groups and clusters in IC 2574 is at most 0.45 pc Myr{sup -1}. The location of the groups found with HOP correlate well with H I contour map features. However, they do not coincide with H I holes, suggesting that those holesmore » were not created by star-forming regions.« less

Scaffold-Based Pan-Agonist Design for the PPARα, PPARβ and PPARγ Receptors

As important members of nuclear receptor superfamily, Peroxisome proliferator-activated receptors (PPAR) play essential roles in regulating cellular differentiation, development, metabolism, and tumorigenesis of higher organisms. The PPAR receptors have 3 identified subtypes: PPARα, PPARβ and PPARγ, all of which have been treated as attractive targets for developing drugs to treat type 2 diabetes. Due to the undesirable side-effects, many PPAR agonists including PPARα/γ and PPARβ/γ dual agonists are stopped by US FDA in the clinical trials. An alternative strategy is to design novel pan-agonist that can simultaneously activate PPARα, PPARβ and PPARγ. Under such an idea, in the current study we adopted the core hopping algorithm and glide docking procedure to generate 7 novel compounds based on a typical PPAR pan-agonist LY465608. It was observed by the docking procedures and molecular dynamics simulations that the compounds generated by the core hopping and glide docking not only possessed the similar functions as the original LY465608 compound to activate PPARα, PPARβ and PPARγ receptors, but also had more favorable conformation for binding to the PPAR receptors. The additional absorption, distribution, metabolism and excretion (ADME) predictions showed that the 7 compounds (especially Cpd#1) hold high potential to be novel lead compounds for the PPAR pan-agonist. Our findings can provide a new strategy or useful insights for designing the effective pan-agonists against the type 2 diabetes.

How to recover Marcus theory with fewest switches surface hopping: Add just a touch of decoherence

We present a slightly improved version of our augmented fewest switches surface hopping (A-FSSH) algorithm and apply it to the calculation of transition rates between diabatic electronic states within the spin-boson model. We compare A-FSSH rates with (i) Marcus rates from the golden rule, (ii) Tully-style FSSH rates, and (iii) FSSH rates using a simple, intuitive decoherence criterion. We show that unlike FSSH, A-FSSH recovers the correct scaling with diabatic coupling (quadratic in V) as well as the lack of dependence on harmonic frequency ω for small enough values of ω and large enough temperatures.

Surface hopping simulation of vibrational predissociation of methanol dimer

The mixed quantum-classical surface hopping method is applied to the vibrational predissociation of methanol dimer, and the results are compared to more exact quantum calculations. Utilizing the vibrational SCF basis, the predissociation problem is cast into a curve crossing problem between dissociative and quasibound surfaces with different vibrational character. The varied features of the dissociative surfaces, arising from the large amplitude OH torsion, generate rich predissociation dynamics. The fewest switches surface hopping algorithm of Tully [J. Chem. Phys. 93, 1061 (1990)] is applied to both diabatic and adiabatic representations. The comparison affords new insight into the criterion for selecting the suitable representation. The adiabatic method's difficulty with low energy trajectories is highlighted. In the normal crossing case, the diabatic calculations yield good results, albeit showing its limitation in situations where tunneling is important. The quadratic scaling of the rates on coupling strength is confirmed. An interesting resonance behavior is identified and is dealt with using a simple decoherence scheme. For low lying dissociative surfaces that do not cross the quasibound surface, the diabatic method tends to overestimate the predissociation rate whereas the adiabatic method is qualitatively correct. Analysis reveals the major culprits involve Rabi-like oscillation, treatment of classically forbidden hops, and overcoherence. Improvements of the surface hopping results are achieved by adopting a few changes to the original surface hopping algorithms.