Jorge Kohanoff

Tchavdar Todorov

Daniel Dundas

Myrta Gruening

Meilan Huang

Ian Lane

Lorenzo Stella

Gareth Tribello

Elton J Santos

Brian Cunningham

Gabriel Greene-Diniz

Malachy Montgomery

Carles Triguero

Mathias Augustin

James Cook

Alejandro de la Calle

Michael Ferguson

Javier Fernández Troncoso

Dale A Hughes

Conrad Johnston

Ryan Kavanagh

Robert Lawrence

Ryan McMillan

Peter Mulholland

Stephen Osborne

Valerio Rizzi

Declan Scullion

Jonathan Smyth

Abigail Wardlow

**Title:**Evaluation of La_{1−x}Sr_{x}MnO_{3}(0 ≤ x < 0.4) synthesised via a modified sol–gel method as mediators for magnetic fluid hyperthermia**Author(s):**McBride K., Cook J., Gray S., Felton S., Stella L., Poulidi D.*CrystEngComm*,**18**, No. 3, pp. 407-416 (21 January 2016)**doi:**10.1039/C5CE01890K**Abstract**

**Full Text**A range of lanthanum strontium manganates (La

_{1−x}Sr_{x}MnO_{3}–LSMO) where 0 ≤ x < 0.4 were prepared using a modified peroxide sol–gel synthesis method. The magnetic nanoparticle (MNP) clusters obtained for each of the materials were characterised using scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and infra-red (IR) spectroscopy in order to confirm the crystalline phases, crystallite size and cluster morphology. The magnetic properties of the materials were assessed using the Superconducting quantum interference device (SQUID) to evaluate the magnetic susceptibility, Curie temperature (Tc) and static hysteretic losses. Induction heating experiments also provided an insight into the magnetocaloric effect for each material. The specific absorption rate (SAR) of the materials was evaluated experimentally and via numerical simulations. The magnetic properties and heating data were linked with the crystalline structure to make predictions with respect to the best LSMO composition for mild hyperthermia (41 °C ≤ T ≤ 46 °C). La_{0.65}Sr_{0.35}MnO_{3}, with crystallite diameter of 82.4 nm, (agglomerate size of ∼10 μm), Tc of 89 °C and SAR of 56 W gMn^{−1}at a concentration 10 mg mL^{−1}gave the optimal induction heating results (Tmax of 46.7 °C) and was therefore deemed as most suitable for the purposes of mild hyperthermia, vide infra.**Title:**Applications of the generalized Langevin equation: Towards a realistic description of the baths**Author(s):**Ness H., Stella L., Lorenz c.D., Kantorovich L.*Physical Review B*,**91**, pp. 014301- (5 January 2015)**doi:**10.1103/PhysRevB.91.014301**Abstract**The generalized Langevin equation (GLE) method, as developed previously [L. Stella et al., Phys. Rev. B 89, 134303 (2014)], is used to calculate the dissipative dynamics of systems described at the atomic level. The GLE scheme goes beyond the commonly used bilinear coupling between the central system and the bath, and permits us to have a realistic description of both the dissipative central system and its surrounding bath. We show how to obtain the vibrational properties of a realistic bath and how to convey such properties into an extended Langevin dynamics by the use of the mapping of the bath vibrational properties onto a set of auxiliary variables. Our calculations for a model of a Lennard-Jones solid show that our GLE scheme provides a stable dynamics, with the dissipative/relaxation processes properly described. The total kinetic energy of the central system always thermalizes toward the expected bath temperature, with appropriate fluctuation around the mean value. More importantly, we obtain a velocity distribution for the individual atoms in the central system which follows the expected canonical distribution at the corresponding temperature. This confirms that both our GLE scheme and our mapping procedure onto an extended Langevin dynamics provide the correct thermostat. We also examined the velocity autocorrelation functions and compare our results with more conventional Langevin dynamics.

**Title:**Real-space grids and the Octopus code as tools for the development of new simulation approaches for electronic systems**Author(s):**Andrade X., Strubbe D., De Giovannini U., Larsen A.H., Oliveira M.J.T., Alberdi-Rodriguez J., Varas A., Theophilou I., Helbig N., Verstraete M.J., Stella L., Nogueira F., Aspuru-Guzik A., Castro A., Marques M.A.L., Rubio A.*Physical Chemistry Chemical Physics*(20 February 2015)**doi:**10.1039/C5CP00351B**Abstract**Real-space grids are a powerful alternative for the simulation of electronic systems. One of the main advantages of the approach is the flexibility and simplicity of working directly in real space where the different fields are discretized on a grid, combined with competitive numerical performance and great potential for parallelization. These properties constitute a great advantage at the time of implementing and testing new physical models. Based on our experience with the Octopus code, in this article we discuss how the real-space approach has allowed for the recent development of new ideas for the simulation of electronic systems. Among these applications are approaches to calculate response properties, modeling of photoemission, optimal control of quantum systems, simulation of plasmonic systems, and the exact solution of the Schrödinger equation for low-dimensionality systems.

**Title:**Generalized Langevin equation: An efficient approach to nonequilibrium molecular dynamics of open systems**Author(s):**Stella L., Lorenz C.D., Kantorovich L.,*Physical Review B*,**89**, pp. 134303- (7 April 2014)**doi:**10.1103/PhysRevB.89.134303**Abstract**The generalized Langevin equation (GLE) has been recently suggested to simulate the time evolution of classical solid and molecular systems when considering general nonequilibrium processes. In this approach, a part of the whole system (an open system), which interacts and exchanges energy with its dissipative environment, is studied. Because the GLE is derived by projecting out exactly the harmonic environment, the coupling to it is realistic, while the equations of motion are non-Markovian. Although the GLE formalism has already found promising applications, e.g., in nanotribology and as a powerful thermostat for equilibration in classical molecular dynamics simulations, efficient algorithms to solve the GLE for realistic memory kernels are highly nontrivial, especially if the memory kernels decay nonexponentially. This is due to the fact that one has to generate a colored noise and take account of the memory effects in a consistent manner. In this paper, we present a simple, yet efficient, algorithm for solving the GLE for practical memory kernels and we demonstrate its capability for the exactly solvable case of a harmonic oscillator coupled to a Debye bath.

**Title:**Performance of Nonlocal Optics When Applied to Plasmonic Nanostructures**Author(s):**Stella L., Zhang P., Garcia-Vidal F.J., Rubio A., Garcia-Gonzalez P.,*The Journal of Physical Chemistry C*,**117**, No. 17, pp. 8941- 8949 (2 May 2013)**doi:**10.1021/jp401887y**Abstract**Semiclassical nonlocal optics based on the hydrodynamic description of conduction electrons might be an adequate tool to study complex phenomena in the emerging field of nanoplasmonics. With the aim of confirming this idea, we obtain the local And nonlocal optical absorption spectra in a model nanoplasmonic device in which there are spatial gaps between the components at nanometric and subnanometric scales. After a comparison against time dependent. density functional calculations, we conclude that hydrodynamic nonlocal optics provides absorption spectra exhibiting qualitative agreement but not quantitative accuracy. This lack of accuracy, which is manifest even in the limit where induced electric currents are not established between the constituents of the device, is mainly due to the poor description of induced electron densities.

**Title:**On transition rates in surface hopping**Author(s):**Escartin J.M., Romaniello P., Stella L., Reinhard P.-G., Suraud E.,*The Journal of Chemical Physics*,**137**, No. 23, Art. No. 234113 ( 21 December 2012)**doi:**10.1063/1.4770280**Abstract**Trajectory surface hopping (TSH) is one of the most widely used quantum-classical algorithms for nonadiabaticmolecular dynamics. Despite its empirical effectiveness and popularity, a rigorous derivation of TSH as the classical limit of a combined quantum electron-nuclear dynamics is still missing. In this work, we aim to elucidate the theoretical basis for the widely used hopping rules. Naturally, we concentrate thereby on the formal aspects of the TSH. Using a Gaussian wave packet limit, we derive the transition rates governing the hopping process at a simple avoided level crossing. In this derivation, which gives insight into the physics underlying the hopping process, some essential features of the standard TSH algorithm are retrieved, namely (i) non-zero electronic transition rate (“hopping probability”) at avoided crossings; (ii) rescaling of the nuclear velocities to conserve total energy; (iii) electronic transition rates linear in the nonadiabatic coupling vectors. The well-known Landau-Zener model is then used for illustration.

**Title:**A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains**Author(s):**Miranda R.P., Fisher A.J, Stella L., Horsfield A.P.,*The Journal of Chemical Physics*,**134**, No. 24, Art. No. 244102 (28 June 2011)**doi:**10.1063/1.3600404**Abstract**Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed.

**Title:**A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. I. General formalism and application to open-shell states**Author(s):**Miranda F.P., Fisher A.J., Stella L., Horsfield A.P.,*The Journal of Chemical Physics*,**134**, No. 24, Art. No. 244101 (28 June 2011)**doi:**10.1063/1.3600397**Abstract**The solution of the time-dependent Schrodinger equation for systems of interacting electrons is generally a prohibitive task, for which approximate methods are necessary. Popular approaches, such as the time-dependent Hartree-Fock (TDHF) approximation and time-dependent density functional theory (TDDFT), are essentially single-configurational schemes. TDHF is by construction incapable of fully accounting for the excited character of the electronic states involved in many physical processes of interest; TDDFT, although exact in principle, is limited by the currently available exchange-correlation functionals. On the other hand, multiconfigurational methods, such as the multiconfigurational time-dependent Hartree-Fock (MCTDHF) approach, provide an accurate description of the excited states and can be systematically improved. However, the computational cost becomes prohibitive as the number of degrees of freedom increases, and thus, at present, the MCTDHF method is only practical for few-electron systems. In this work, we propose an alternative approach which effectively establishes a compromise between efficiency and accuracy, by retaining the smallest possible number of configurations that catches the essential features of the electronic wavefunction. Based on a time-dependent variational principle, we derive the MCTDHF working equation for a multiconfigurational expansion with fixed coefficients and specialise to the case of general open-shell states, which are relevant for many physical processes of interest.

**Title:**Analog of Rabi oscillations in resonant electron-ion systems**Author(s):**Stella L., Miranda R.P., Horsfield A.P., Fisher A.J.,*The Journal of Chemical Physics*,**134**, No. 19, Art. No. 194105 (21 May 2011)**doi:**10.1063/1.3589165**Abstract**Quantum coherence between electron and ion dynamics, observed in organic semiconductors by means of ultrafast spectroscopy, is the object of recent theoretical and computational studies. To simulate this kind of quantum coherent dynamics, we have introduced in a previous article [L. Stella, M. Meister, A. J. Fisher, and A. P. Horsfield, J. Chem. Phys. 127, 214104 (2007)] an improved computational scheme based on Correlated Electron-Ion Dynamics (CEID). In this article, we provide a generalization of that scheme to model several ionic degrees of freedom and many-body electronic states. To illustrate the capability of this extended CEID, we study a model system which displays the electron-ion analog of the Rabi oscillations. Finally, we discuss convergence and scaling properties of the extended CEID along with its applicability to more realistic problems

**Title:**Strong electronic correlation in the hydrogen chain: A variational Monte Carlo study**Author(s):**Stella L., Attaccalite C., Sorella S., Rubio A.,*Physical Review B*,**84**, No. 24, Art. No. 245117 (14 December 2011)**doi:**10.1103/PhysRevB.84.245117**Abstract**In this paper, we report a fully ab initio variational Monte Carlo study of the linear and periodic chain of hydrogen atoms, a prototype system providing the simplest example of strong electronic correlation in low dimensions. In particular, we prove that numerical accuracy comparable to that of benchmark density-matrix renormalization-group calculations can be achieved by using a highly correlated Jastrow-antisymmetrized geminal power variational wave function. Furthermore, by using the so-called "modern theory of polarization" and by studying the spin-spin and dimer-dimer correlations functions, we have characterized in detail the crossover between the weakly and strongly correlated regimes of this atomic chain. Our results show that variational Monte Carlo provides an accurate and flexible alternative to highly correlated methods of quantum chemistry which, at variance with these methods, can be also applied to a strongly correlated solid in low dimensions close to a crossover or a phase transition.

**Title:**Modelling non-adiabatic processes using correlated electron-ion dynamics**Author(s):**McEniry E.J., Wang Y., Dundas D., Todorov T.N., Stella L., Miranda R.P., Fisher A.J., Horsfield A.P., Race C.P., Mason D.R., Foulkes W.M.C., Sutton A.P.*European Physical Journal B*,**77**, No. 3, pp. 305-329 (October 2010)**doi:**10.1140/epjb/e2010-00280-5**Abstract**Here we survey the theory and applications of a family of methods (correlated electron-ion dynamics, or CEID) that can be applied to a diverse range of problems involving the non-adiabatic exchange of energy between electrons and nuclei. The simplest method, which is a paradigm for the others, is Ehrenfest Dynamics. This is applied to radiation damage in metals and the evolution of excited states in conjugated polymers. It is unable to reproduce the correct heating of nuclei by current carrying electrons, so we introduce a moment expansion that allows us to restore the spontaneous emission of phonons. Because of the widespread use of Non-Equilibrium Green's Functions for computing electric currents in nanoscale systems, we present a comparison of this formalism with that of CEID with open boundaries. When there is strong coupling between electrons and nuclei, the moment expansion does not converge. We thus conclude with a reworking of the CEID formalism that converges systematically and in a stable manner.

**Title:**Correlated electron-ion dynamics in metallic systems**Author(s):**Horsfield A.P., Finnis M., Foulkes M., LePage J., Mason D., Race C., Sutton A.P., Bowler D.R., Fisher A.J., Miranda R., Stella L., Stoneham A.M., Dundas D., McEniry E., Todorov T.N., Sanchez C.G.,*Computational Materials Science*,**44**, No. 1, pp. 16-20 (November 2008)**doi:**10.1016/j.commatsci.2008.01.055**Abstract**In this paper we briefly discuss the problem of simulating non-adiabatic processes in systems that are usefully modelled using molecular dynamics. In particular we address the problems associated with metals, and describe two methods that can be applied: the Ehrenfest approximation and correlated electron-ion dynamics (CEID). The Ehrenfest approximation is used to successfully describe the friction force experienced by an energetic particle passing through a crystal, but is unable to describe the heating of a wire by an electric current. CEID restores the proper heating. (C) 2008 Elsevier B.V. All rights reserved.

**Title:**Robust nonadiabatic molecular dynamics for metals and insulators**Author(s):**Stella L., Meister M., Fisher A. J., Horsfield A. P.*Journal of Physical Chemistry*,**127**, No. 21, Art. No. 214104 (4 December 2007)**doi:**10.1063/1.2801537**Abstract**We present a new formulation of the correlated electron-ion dynamics (CEID) scheme, which systematically improves Ehrenfest dynamics by including quantum fluctuations around the mean-field atomic trajectories. We show that the method can simulate models of nonadiabatic electronic transitions and test it against exact integration of the time-dependent Schrödinger equation. Unlike previous formulations of CEID, the accuracy of this scheme depends on a single tunable parameter which sets the level of atomic fluctuations included. The convergence to the exact dynamics by increasing the tunable parameter is demonstrated for a model two level system. This algorithm provides a smooth description of the nonadiabatic electronic transitions which satisfies the kinematic constraints (energy and momentum conservation) and preserves quantum coherence. The applicability of this algorithm to more complex atomic systems is discussed.

**Title:**Quantum annealing of an ising spin-glass by Green's function Monte Carlo**Author(s):**Stella L., Santoro G.E.,*Physical Review E*,**75**, No. 3, Art. No. 036703 (March 2007)**doi:**10.1103/PhysRevE.75.036703**Abstract**We present an implementation of quantum annealing (QA) via lattice Green's function Monte Carlo (GFMC), focusing on its application to the Ising spin glass in transverse field. In particular, we study whether or not such a method is more effective than the path-integral Monte Carlo- (PIMC) based QA, as well as classical simulated annealing (CA), previously tested on the same optimization problem. We identify the issue of importance sampling, i.e., the necessity of possessing reasonably good (variational) trial wave functions, as the key point of the algorithm. We performed GFMC-QA runs using such a Boltzmann-type trial wave function, finding results for the residual energies that are qualitatively similar to those of CA (but at a much larger computational cost), and definitely worse than PIMC-QA. We conclude that, at present, without a serious effort in constructing reliable importance sampling variational wave functions for a quantum glass, GFMC-QA is not a true competitor of PIMC-QA.

**Title:**Monte Carlo studies of quantum and classical annealing on a double well**Author(s):**Stella L., Santoro G.E., Tosatti E.,*Physical Review B*,**73**, No. 14, Art. No. 144302 (April 2006)**doi:**10.1103/PhysRevB.73.144302**Abstract**We present results for a variety of Monte Carlo annealing approaches, both classical and quantum, benchmarked against one another for the textbook optimization exercise of a simple one-dimensional double well. In classical (thermal) annealing, the dependence upon the move chosen in a Metropolis scheme is studied and correlated with the spectrum of the associated Markov transition matrix. In quantum annealing, the path integral Monte Carlo approach is found to yield nontrivial sampling difficulties associated with the tunneling between the two wells. The choice of fictitious quantum kinetic energy is also addressed. We find that a "relativistic" kinetic energy form, leading to a higher probability of long real-space jumps, can be considerably more effective than the standard nonrelativistic one.

**Title:**Optimization through quantum annealing: theory and some applications**Author(s):**Battaglia D.A., Stella L.,*Contemporary Physics*,**47**, No. 4, pp. 195-208 (July-August 2006)**doi:**10.1080/00107510600861454**Abstract**Quantum annealing is a promising tool for solving optimization problems, similar in some ways to the traditional ( classical) simulated annealing of Kirkpatrick et al. Simulated annealing takes advantage of thermal fluctuations in order to explore the optimization landscape of the problem at hand, whereas quantum annealing employs quantum fluctuations. Intriguingly, quantum annealing has been proved to be more effective than its classical counterpart in many applications. We illustrate the theory and the practical implementation of both classical and quantum annealing - highlighting the crucial differences between these two methods - by means of results recently obtained in experiments, in simple toy-models, and more challenging combinatorial optimization problems ( namely, Random Ising model and Travelling Salesman Problem). The techniques used to implement quantum and classical annealing are either deterministic evolutions, for the simplest models, or Monte Carlo approaches, for harder optimization tasks. We discuss the pro and cons of these approaches and their possible connections to the landscape of the problem addressed.

**Title:**Optimization by quantum annealing: Lessons from simple cases**Author(s):**Stella L., Santoro G.E., Tosatti E.,*Physical Review B*,**72**, No. 1, Art. No. 014303 (July 2005)**doi:**10.1103/PhysRevB.72.014303**Abstract**We investigate the basic behavior and performance of simulated quantum annealing (QA) in comparison with classical annealing (CA). Three simple one-dimensional case study systems are considered: namely, a parabolic well, a double well, and a curved washboard. The time-dependent Schrodinger evolution in either real or imaginary time describing QA is contrasted with the Fokker-Planck evolution of CA. The asymptotic decrease of excess energy with annealing time is studied in each case, and the reasons for differences are examined and discussed. The Huse-Fisher classical power law of double-well CA is replaced with a different power law in QA. The multiwell washboard problem studied in CA by Shinomoto and Kabashima and leading classically to a logarithmic annealing even in the absence of disorder turns to a power-law behavior when annealed with QA. The crucial role of disorder and localization is briefly discussed.

**Title:**Theory of phonon dissipation in the conduction of stressed Au nanowires**Author(s):**Stella L., Santoro G.E., Fabrizio M., Tosatti E,*Surface Science*,**566**, No. 1, pp. 430-435 (20 September 2004)**doi:**10.1016/j.susc.2004.06.121**Abstract**Recent experiments on Au break junctions [Phys. Rev. Lett. 88 (2002) 216803] have characterized the nonlinear conductance of stretched short Au nanowires. They reveal in the voltage range 10-20 meV the signatures of dissipation effects, likely due to phonons in the nanowire, reducing the conductance below the quantized value of 2e(2)/h. We present here a theory, based on a model tight-binding Hamiltonian and on non-equilibrium Green's function techniques, which accounts for the main features of the experiment. The theory helps in revealing details of the experiment which need to be addressed with a more realistic, less idealized, theoretical framework.