29 research outputs found
Comment on "Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction" [J. Chem. Phys. 137, 22A530 (2012)]
In spite of the relevance of the proposal introduced in the recent work A.
Abedi, N. T. Maitra and E. K. U. Gross, J. Chem. Phys. 137, 22A530, 2012, there
is an important ingredient which is missing. Namely, the proof that the norms
of the electronic and nuclear wavefunctions which are the solutions to the
nonlinear equations of motion are preserved by the evolution. To prove the
conservation of these norms is precisely the objective of this Comment.Comment: 2 pages, published versio
Nonextensive thermodynamic functions in the Schr\"odinger-Gibbs ensemble
Schr\"odinger suggested that thermodynamical functions cannot be based on the
gratuitous allegation that quantum-mechanical levels (typically the orthogonal
eigenstates of the Hamiltonian operator) are the only allowed states for a
quantum system [E. Schr\"odinger, Statistical Thermodynamics (Courier Dover,
Mineola, 1967)]. Different authors have interpreted this statement by
introducing density distributions on the space of quantum pure states with
weights obtained as functions of the expectation value of the Hamiltonian of
the system.
In this work we focus on one of the best known of these distributions, and we
prove that, when considered in composite quantum systems, it defines partition
functions that do not factorize as products of partition functions of the
noninteracting subsystems, even in the thermodynamical regime. This implies
that it is not possible to define extensive thermodynamical magnitudes such as
the free energy, the internal energy or the thermodynamic entropy by using
these models. Therefore, we conclude that this distribution inspired by
Schr\"odinger's idea can not be used to construct an appropriate quantum
equilibrium thermodynamics.Comment: 32 pages, revtex 4.1 preprint style, 5 figures. Published version
with several changes with respect to v2 in text and reference
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 , and on the number of classical
trajectories of the initial distribution. The results in this work open new
perspectives for studying decoherence with Ehrenfest dynamics.Comment: Revtex 4-1, 14 pages, 2 figures. Final published versio
Efficient formalism for large scale ab initio molecular dynamics based on time-dependent density functional theory
A new "on the fly" method to perform Born-Oppenheimer ab initio molecular
dynamics (AIMD) is presented. Inspired by Ehrenfest dynamics in time-dependent
density functional theory, the electronic orbitals are evolved by a
Schroedinger-like equation, where the orbital time derivative is multiplied by
a parameter. This parameter controls the time scale of the fictitious
electronic motion and speeds up the calculations with respect to standard
Ehrenfest dynamics. In contrast to other methods, wave function orthogonality
needs not be imposed as it is automatically preserved, which is of paramount
relevance for large scale AIMD simulations.Comment: 5 pages, 3 color figures, revtex4 packag
An exact expression to calculate the derivatives of position-dependent observables in molecular simulations with flexible constraints
In this work, we introduce an algorithm to compute the derivatives of
physical observables along the constrained subspace when flexible constraints
are imposed on the system (i.e., constraints in which the hard coordinates are
fixed to configuration-dependent values). The presented scheme is exact, it
does not contain any tunable parameter, and it only requires the calculation
and inversion of a sub-block of the Hessian matrix of second derivatives of the
function through which the constraints are defined. We also present a practical
application to the case in which the sought observables are the Euclidean
coordinates of complex molecular systems, and the function whose minimization
defines the constraints is the potential energy. Finally, and in order to
validate the method, which, as far as we are aware, is the first of its kind in
the literature, we compare it to the natural and straightforward
finite-differences approach in three molecules of biological relevance:
methanol, N-methyl-acetamide and a tri-glycine peptideComment: 13 pages, 8 figures, published versio
Statistics and Nos\'e formalism for Ehrenfest dynamics
Quantum dynamics (i.e., the Schr\"odinger 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 Nos\'e (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.Comment: 28 pages, 1 figure. Published version. arXiv admin note: substantial
text overlap with arXiv:1010.149
Ab Initio Molecular Dynamics on the Electronic Boltzmann Equilibrium Distribution
We prove that for a combined system of classical and quantum particles, it is
possible to write a dynamics for the classical particles that incorporates in a
natural way the Boltzmann equilibrium population for the quantum subsystem. In
addition, these molecular dynamics do not need to assume that the electrons
immediately follow the nuclear motion (in contrast to any adiabatic approach),
and do not present problems in the presence of crossing points between
different potential energy surfaces (conical intersections or spin-crossings).
A practical application of this molecular dynamics to study the effect of
temperature in molecular systems presenting (nearly) degenerate states - such
as the avoided crossing in the ring-closure process of ozone - is presented.Comment: published in New J. Phy
On the Coulomb-dipole transition in mesoscopic classical and quantum electron-hole bilayers
We study the Coulomb-to-dipole transition which occurs when the separation
of an electron-hole bilayer system is varied with respect to the
characteristic in-layer distances. An analysis of the classical ground state
configurations for harmonically confined clusters with reveals that
the energetically most favorable state can differ from that of two-dimensional
pure dipole or Coulomb systems. Performing a normal mode analysis for the N=19
cluster it is found that the lowest mode frequencies exhibit drastic changes
when is varied. Furthermore, we present quantum-mechanical ground states
for N=6, 10 and 12 spin-polarized electrons and holes. We compute the
single-particle energies and orbitals in self-consistent Hartree-Fock
approximation over a broad range of layer separations and coupling strengths
between the limits of the ideal Fermi gas and the Wigner crystal
A mathematical and computational review of Hartree-Fock SCF methods in Quantum Chemistry
We present here a review of the fundamental topics of Hartree-Fock theory in
Quantum Chemistry. From the molecular Hamiltonian, using and discussing the
Born-Oppenheimer approximation, we arrive to the Hartree and Hartree-Fock
equations for the electronic problem. Special emphasis is placed in the most
relevant mathematical aspects of the theoretical derivation of the final
equations, as well as in the results regarding the existence and uniqueness of
their solutions. All Hartree-Fock versions with different spin restrictions are
systematically extracted from the general case, thus providing a unifying
framework. Then, the discretization of the one-electron orbitals space is
reviewed and the Roothaan-Hall formalism introduced. This leads to a exposition
of the basic underlying concepts related to the construction and selection of
Gaussian basis sets, focusing in algorithmic efficiency issues. Finally, we
close the review with a section in which the most relevant modern developments
(specially those related to the design of linear-scaling methods) are commented
and linked to the issues discussed. The whole work is intentionally
introductory and rather self-contained, so that it may be useful for non
experts that aim to use quantum chemical methods in interdisciplinary
applications. Moreover, much material that is found scattered in the literature
has been put together here to facilitate comprehension and to serve as a handy
reference.Comment: 64 pages, 3 figures, tMPH2e.cls style file, doublesp, mathbbol and
subeqn package