RESUMEN
In this publication, we propose a new set of reactivity/selectivity descriptors, derived within a Rayleigh-Schrödinger perturbation theory framework, for chemical systems undergoing an electrostatic (point-charge) perturbation. From the electron density polarization at first order, qualitative insight on reactivity is retrieved, while more quantitative information (noteworthy selectivity) can be obtained from either the second-order energy response or the number of shifted electrons under perturbation. Noteworthily, only a small number of excitations contribute significantly to the overall responses to perturbation, suggesting chemical reactivity could be foreseen by a careful scrutiny of the electron density reorganization upon excitation.
RESUMEN
The correlated spin dynamics and temperature dependence of the correlation length xi(T) in two-dimensional quantum (S = 1/2) Heisenberg antiferromagnets (2DQHAF) on a square lattice are discussed in light of experimental results of proton spin lattice relaxation in copper formiate tetradeuterate. In this compound the exchange constant is much smaller than the one in recently studied 2DQHAF, such as La2CuO4 and Sr2CuO2Cl2. Thus the spin dynamics can be probed in detail over a wider temperature range. The NMR relaxation rates turn out to be in excellent agreement with a theoretical mode-coupling calculation. The deduced temperature behavior of xi(T) is in agreement with high-temperature expansions, quantum Monte Carlo simulations, and the pure quantum self-consistent harmonic approximation. Contrary to the predictions of the theories based on the nonlinear sigma model, no evidence of crossover between different quantum regimes is observed.
RESUMEN
The standard system-plus-reservoir approach used in the study of dissipative systems can be meaningfully generalized to a dissipative coupling involving the momentum, instead of the coordinate: the corresponding equation of motion differs from the Langevin equation, so this is called anomalous dissipation. It occurs for systems where such coupling can indeed be derived from the physical analysis of the degrees of freedom that can be treated as a dissipation bath. Starting from the influence functional corresponding to anomalous dissipation, it is shown how to derive the effective classical potential that gives the quantum thermal averages for the dissipative system in terms of classical-like calculations; the generalization to many degrees of freedom is given. The formalism is applied to a single particle in a double well and to the discrete phi(4) model. At variance with the standard case, the fluctuations of the coordinate are enhanced by anomalous dissipative coupling.