arXiv subjects

J. Clemente-Gallardo

Publications and source records attributed to J. Clemente-Gallardo.

35 records · Page 2Linked to original sources

arXiv2012

Non-adiabatic effects within a single thermally-averaged potential energy surface: Thermal expansion and reaction rates of small molecules

At non-zero temperature and when a system has low-lying excited electronic states, the ground-state Born--Oppenheimer approximation breaks down and the low-lying electronic states are involved in any chemical process. In this work, we use a temperature-dependent effective potential for the nuclei which can accomodate the influence of an arbitrary number of electronic states in a simple way, while at the same time producing the correct Boltzmann equibrium distribution for the electronic part. With the help of this effective potential, we show that thermally-activated low-lying electronic states can have a significant effect in molecular properties for which electronic excitations are oftentimes ignored. We study the thermal expansion of the Manganese dimer, Mn$_2$, where we find that the average bond length experiences a change larger than the present experimental accuracy upon the inclusion of the excited states into the picture. We also show that, when these states are taken into account, reaction rate constants are modified. In particular, we study the opening of the ozone molecule, O$_3$, and show that in this case the rate is modified as much as a 20% with respect to the ground-state Born--Oppenheimer prediction.

physics.chem-ph↗

arXiv2012

Ehrenfest dynamics is purity non-preserving: a necessary ingredient for decoherence

We discuss the evolution of purity in mixed quantum/classical approaches to electronic nonadiabatic dynamics in the context of the Ehrenfest model. As it is impossible to exactly determine initial conditions for a realistic system, we choose to work in the statistical Ehrenfest formalism that we introduced in Ref. 1. From it, we develop a new framework to determine exactly the change in the purity of the quantum subsystem along the evolution of a statistical Ehrenfest system. In a simple case, we verify how and to which extent Ehrenfest statistical dynamics makes a system with more than one classical trajectory and an initial quantum pure state become a quantum mixed one. We prove this numerically showing how the evolution of purity depends on time, on the dimension of the quantum state space $D$, and on the number of classical trajectories $N$ of the initial distribution. The results in this work open new perspectives for studying decoherence with Ehrenfest dynamics.

physics.chem-ph↗

arXiv2012

Tensorial characterization and quantum estimation of weakly entangled qubits

In the case of two qubits, standard entanglement monotones like the linear entropy fail to provide an efficient quantum estimation in the regime of weak entanglement. In this paper, a more efficient entanglement estimation, by means of a novel class of entanglement monotones, is proposed. Following an approach based on the geometric formulation of quantum mechanics, these entanglement monotones are defined by inner products on invariant tensor fields on bipartite qubit orbits of the group SU(2)xSU(2).

quant-ph↗

arXiv2011

Statistics and Nosé formalism for Ehrenfest dynamics

Quantum dynamics (i.e., the Schrödinger equation) and classical dynamics (i.e., Hamilton equations) can both be formulated in equal geometric terms: a Poisson bracket defined on a manifold. In this paper we first show that the hybrid quantum-classical dynamics prescribed by the Ehrenfest equations can also be formulated within this general framework, what has been used in the literature to construct propagation schemes for Ehrenfest dynamics. Then, the existence of a well defined Poisson bracket allows to arrive to a Liouville equation for a statistical ensemble of Ehrenfest systems. The study of a generic toy model shows that the evolution produced by Ehrenfest dynamics is ergodic and therefore the only constants of motion are functions of the Hamiltonian. The emergence of the canonical ensemble characterized by the Boltzmann distribution follows after an appropriate application of the principle of equal a priori probabilities to this case. Once we know the canonical distribution of a Ehrenfest system, it is straightforward to extend the formalism of Nosé (invented to do constant temperature Molecular Dynamics by a non-stochastic method) to our Ehrenfest formalism. This work also provides the basis for extending stochastic methods to Ehrenfest dynamics.

physics.chem-ph↗

arXiv2011

Some applications of quasi-velocities in optimal control

In this paper we study optimal control problems for nonholonomic systems defined on Lie algebroids by using quasi-velocities. We consider both kinematic, i.e. systems whose cost functional depends only on position and velocities, and dynamic optimal control problems, i.e. systems whose cost functional depends also on accelerations. The formulation of the problem directly at the level of Lie algebroids turns out to be the correct framework to explain in detail similar results appeared recently (Maruskin and Bloch, 2007). We also provide several examples to illustrate our construction.

math.OC↗

arXiv2011

From Geometric Quantum Mechanics to Quantum Information

We consider the geometrization of quantum mechanics. We then focus on the pull-back of the Fubini-Study metric tensor field from the projective Hibert space to the orbits of the local unitary groups. An inner product on these tensor fields allows us to obtain functions which are invariant under the considered local unitary groups. This procedure paves the way to an algorithmic approach to the identification of entanglement monotone candidates. Finally, a link between the Fubini-Study metric and a quantum version of the Fisher information metric is discussed.

math-ph↗

arXiv2010

Classical Tensors and Quantum Entanglement II: Mixed States

Invariant operator-valued tensor fields on Lie groups are considered. These define classical tensor fields on Lie groups by evaluating them on a quantum state. This particular construction, applied on the local unitary group U(n)xU(n), may establish a method for the identification of entanglement monotone candidates by deriving invariant functions from tensors being by construction invariant under local unitary transformations. In particular, for n=2, we recover the purity and a concurrence related function (Wootters 1998) as a sum of inner products of symmetric and anti-symmetric parts of the considered tensor fields. Moreover, we identify a distinguished entanglement monotone candidate by using a non-linear realization of the Lie algebra of SU(2)xSU(2). The functional dependence between the latter quantity and the concurrence is illustrated for a subclass of mixed states parametrized by two variables.

math-ph↗

arXiv2010

Geometry and Statistics of Ehrenfest dynamics

Quantum dynamics (e.g., the Schrödinger equation) and classical dynamics (e.g., Hamilton equations) can both be formulated in equal geometric terms: a Poisson bracket defined on a manifold. The difference between both worlds is due to the presence of extra structure in the quantum case, that leads to the appearance of the probabilistic nature of the measurements and the indetermination and superposition principles. In this paper we first show that the quantum-classical dynamics prescribed by the Ehrenfest equations can also be formulated within this general framework, what has been used in the literature to construct propagation schemes for Ehrenfest dynamics. Then, the existence of a well defined Poisson bracket allows to arrive to a Liouville equation for a statistical ensemble of Ehrenfest systems. The study of a generic toy model shows that the evolution produced by Ehrenfest dynamics is ergodic and therefore the only constants of motion are functions of the Hamiltonian. The emergence of the canonical ensemble characterized by the Boltzmann's distribution follows after an appropriate application of the principle of equal a priori probabilities to this case. This work provides the basis for extending stochastic methods to Ehrenfest dynamics.

quant-ph↗

arXiv2009

Classical Tensors and Quantum Entanglement I: Pure States

The geometrical description of a Hilbert space asociated with a quantum system considers a Hermitian tensor to describe the scalar inner product of vectors which are now described by vector fields. The real part of this tensor represents a flat Riemannian metric tensor while the imaginary part represents a symplectic two-form. The immersion of classical manifolds in the complex projective space associated with the Hilbert space allows to pull-back tensor fields related to previous ones, via the immersion map. This makes available, on these selected manifolds of states, methods of usual Riemannian and symplectic geometry. Here we consider these pulled-back tensor fields when the immersed submanifold contains separable states or entangled states. Geometrical tensors are shown to encode some properties of these states. These results are not unrelated with criteria already available in the literature. We explicitly deal with some of these relations.

math-ph↗

arXiv2008

Towards a definition of quantum integrability

We briefly review the most relevant aspects of complete integrability for classical systems and identify those aspects which should be present in a definition of quantum integrability. We show that a naive extension of classical concepts to the quantum framework would not work because all infinite dimensional Hilbert spaces are unitarily isomorphic and, as a consequence, it would not be easy to define degrees of freedom. We argue that a geometrical formulation of quantum mechanics might provide a way out.

math-ph↗

arXiv2008

Basics of Quantum Mechanics, Geometrization and some Applications to Quantum Information

In this paper we present a survey of the use of differential geometric formalisms to describe Quantum Mechanics. We analyze Schrödinger framework from this perspective and provide a description of the Weyl-Wigner construction. Finally, after reviewing the basics of the geometric formulation of quantum mechanics, we apply the methods presented to the most interesting cases of finite dimensional Hilbert spaces: those of two, three and four level systems (one qubit, one qutrit and two qubit systems). As a more practical application, we discuss the advantages that the geometric formulation of quantum mechanics can provide us with in the study of situations as the functional independence of entanglement witnesses.

quant-ph↗

arXiv2007

Boundary conditions: The path integral approach

The path integral approach to quantum mechanics requires a substantial generalisation to describe the dynamics of systems confined to bounded domains. Non-local boundary conditions can be introduced in Feynman's approach by means of boundary amplitude distributions and complex phases to describe the quantum dynamics in terms of the classical trajectories. The different prescriptions involve only trajectories reaching the boundary and correspond to different choices of boundary conditions of selfadjoint extensions of the Hamiltonian. One dimensional particle dynamics is analysed in detail.

quant-ph↗

arXiv2007

Reduction Procedures in Classical and Quantum Mechanics

We present, in a pedagogical style, many instances of reduction procedures appearing in a variety of physical situations, both classical and quantum. We concentrate on the essential aspects of any reduction procedure, both in the algebraic and geometrical setting, elucidating the analogies and the differences between the classical and the quantum situations.

math-ph↗

arXiv2007

The space of density states in geometrical quantum mechanics

We present a geometrical description of the space of density states of a quantum system of finite dimension. After presenting a brief summary of the geometrical formulation of Quantum Mechanics, we proceed to describe the space of density states $\D(\Hil)$ from a geometrical perspective identifying the stratification associated to the natural $GL(\Hil)$--action on $\D(\Hil)$ and some of its properties. We apply this construction to the cases of quantum systems of two and three levels.

quant-ph↗

arXiv2007

Introduction to Quantum Mechanics and the Quantum-Classical transition

In this paper we present a survey of the use of differential geometric formalisms to describe Quantum Mechanics. We analyze Schroedinger and Heisenberg frameworks from this perspective and discuss how the momentum map associated to the action of the unitary group on the Hilbert space allows to relate both approaches. We also study Weyl-Wigner approach to Quantum Mechanics and discuss the implications of bi-Hamiltonian structures at the quantum level.

quant-ph↗

arXiv2007

Geometrization of Quantum Mechanics

We show that it is possible to represent various descriptions of Quantum Mechanics in geometrical terms. In particular we start with the space of observables and use the momentum map associated with the unitary group to provide an unified geometrical description for the different pictures of Quantum Mechanics. This construction provides an alternative to the usual GNS construction for pure states.

math-ph↗

arXiv1996

Antiferromagnetism in four dimensions: search for non-triviality

We present antiferromagnetism as a mechanism capable of modifying substantially the phase diagram and the critical behaviour of statistical mechanical models. This is particularly relevant in four dimensions, due to the connection between second order transition points and the continuum limit as a quantum field theory. We study three models with an antiferromagnetic interaction: the Ising and the O(4) Models with a second neighbour negative coupling, and the $\RP{2}$ Model. Different conclusions are obtained depending on the model.

hep-lat↗