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The key factors that distinguish algorithms for nonadiabatic mixed quantum/classical (MQC) simulations from each other are how they incorporate quantum decoherence-the fact that classical nuclei must eventually cause a quantum superposition state to collapse into a pure state-and how they model the effects of decoherence on the quantum and classical subsystems. Most algorithms use distinct mechanisms for modeling nonadiabatic transitions between pure quantum basis states ("surface hops") and for calculating the loss of quantum-mechanical phase information (e.g., the decay of the off-diagonal elements of the density matrix). In our view, however, both processes should be unified in a single description of decoherence. In this paper, we start from the density matrix of the total system and use the frozen Gaussian approximation for the nuclear wave function to derive a nuclear-induced decoherence rate for the electronic degrees of freedom. We then use this decoherence rate as the basis for a new nonadiabatic MQC molecular-dynamics (MD) algorithm, which we call mean-field dynamics with stochastic decoherence (MF-SD). MF-SD begins by evolving the quantum subsystem according to the time-dependent Schrodinger equation, leading to mean-field dynamics. MF-SD then uses the nuclear-induced decoherence rate to determine stochastically at each time step whether the system remains in a coherent mixed state or decoheres. Once it is determined that the system should decohere, the quantum subsystem undergoes an instantaneous total wave-function collapse onto one of the adiabatic basis states and the classical velocities are adjusted to conserve energy. Thus, MF-SD combines surface hops and decoherence into a single idea: decoherence in MF-SD does not require the artificial introduction of reference states, auxiliary trajectories, or trajectory swarms, which also makes MF-SD much more computationally efficient than other nonadiabatic MQC MD algorithms. The unified definition of decoherence in MF-SD requires only a single ad hoc parameter, which is not adjustable but instead is determined by the spatial extent of the nonadiabatic coupling. We use MF-SD to solve a series of one-dimensional scattering problems and find that MF-SD is as quantitatively accurate as several existing nonadiabatic MQC MD algorithms and significantly more accurate for some problems. (c) 2005 American Institute of Physics.

In polar fluids such as water and methanol, the peak of the solvated electron's absorption spectrum in the red has been assigned as a sum of transitions between an s-like ground state and three nearly degenerate p-like excited states bound in a quasispherical cavity. In contrast, in weakly polar solvents such as tetrahydrofuran (THF), the solvated electron has an absorption spectrum that peaks in the mid-infrared, but no definitive assignment has been offered about the origins of the spectrum or the underlying structure. In this paper, we present the results of adiabatic mixed quantum/classical molecular dynamic simulations of the solvated electron in THF, and provide a detailed explanation of the THF-solvated electron's absorption spectrum and electronic structure. Using a classical solvent model and a fully quantum mechanical excess electron, our simulations show that although the ground and first excited states are bound in a quasispherical cavity, a multitude of other, nearby solvent cavities support numerous, nearly degenerate, bound excited states that have little Franck-Condon overlap with the ground state. We show that these solvent cavities, which are partially polarized so that they act as electron trapping sites, are an inherent property of the way THF molecules pack in the liquid. The absorption spectrum is thus assigned to a sum of bound-to-bound transitions between a localized ground state and multiple disjoint excited states scattered throughout the fluid. Furthermore, we find that the usual spherical harmonic labels (e.g., s-like, p-like) are not good descriptors of the excited-state wave functions of the solvated electron in THF. Our observation of multiple disjoint excited states is consistent with femtosecond pump-probe experiments in the literature that suggest that photoexcitation of solvated electrons in THF causes them to relocalize into solvent cavities far from where they originated. (C) 2005 American Institute of Physics.

Since charge-transfer-to-solvent (CTTS) reactions represent the simplest class of solvent-driven electron transfer reactions, there has been considerable interest in understanding the solvent motions responsible for electron ejection. The major question that we explore in this paper is what role the symmetry of the electronic states plays in determining the solvent motions that account for CTTS. To this end, we have performed a series of one-electron mixed quantum/classical nonadiabatic molecular dynamics simulations of the CTTS dynamics of sodide, Na-, which has its ground-state electron in an s orbital and solvent-supported CTTS excited states of p-like symmetry. We compare our simulations to previous theoretical work on the CTTS dynamics of the aqueous halides, in which the ground state has the electron in a p orbital and the CTTS excited state has s-like symmetry. We find that the key motions for Na- relaxation involve translations of solvent molecules into the node of the p-like CTTS excited state. This solvation of the electronic node leads to migration of the excited CTTS electron, leaving one of the p-like lobes pinned to the sodium atom core and the other extended into the solvent; this nodal migration causes a breakdown of linear response. Most importantly, for the nonadiabatic transition out of the CTTS excited state and the subsequent return to equilibrium, we find dramatic differences between the relaxation dynamics of sodide and the halides that result directly from differences in electronic symmetry. Since the ground state of the ejected electron is s-like, detachment from the s-like CTTS excited state of the halides occurs directly, but detachment cannot occur from the p-like CTTS excited state of Na- without a nonadiabatic transition to remove the node. Thus, unlike the halides, CTTS electron detachment from sodide occurs only after relaxation to the ground state and is a relatively rare event. In addition, the fact that the electronic symmetry of sodide is the same as for the hydrated electron enables us to directly study the effect of a stabilizing atomic core on the properties and solvation dynamics of solvent-supported electronic states. All the results are compared to experimental work on Na- CTTS dynamics, and a unified picture for the electronic relaxation for solvent-supported excited states of any symmetry is presented. (C) 2003 American Institute of Physics.

We introduce an efficient configuration interaction (CI) method for the calculation of mixed quantum and classical nonadiabatic molecular dynamics for multiple electrons. For any given realization of the classical degrees of freedom (e.g., a solvent), the method uses a novel real-space quadrature to efficiently compute the Coulomb and exchange interactions between electrons. We also introduce an approximation whereby the classical molecular dynamics is propagated for several time steps on electronic potential energy surfaces generated using only a particularly important subset of the CI basis states. By only updating the important-states subset periodically, we achieve significant reductions in the computational cost of solving the multielectron quantum problem. We test the real-space quadrature for the cases of two electrons confined in a cubic box with infinitely repulsive walls and two electrons dissolved in liquid water that occupy a single cavity, so-called hydrated dielectrons. We then demonstrate how to perform mixed quantum and classical nonadiabatic dynamics by combining these computational techniques with the mean-field with surface hopping algorithm of Prezhdo and Rossky [J. Chem. Phys. 107, 825 (1997)]. Finally, we illustrate the practicality of the approach to multielectron nonadiabatic dynamics by examining the nonadiabatic relaxation dynamics of both spin singlet and spin triplet hydrated dielectrons following excitation from the ground to the first excited state. (C) 2003 American Institute of Physics.

The Cryogenic Underground Observatory for Rare Events (CUORE) is the first cryogenic experiment searching for neutrinoless double-beta (0vßß) decay that has been able to reach the one-ton scale. The detector, located at the Laboratori Nazionali del Gran Sasso in Italy, consists of an array of 988 TeO2 crystals arranged in a compact cylindrical structure of 19 towers. Following the completion of the detector construction in August 2016, CUORE began its first physics data run in 2017 at a base temperature of about 10 mK. Following multiple optimization campaigns in 2018, CUORE is currently in stable operating mode. In 2019, CUORE released its 2nd result of the search for 0vßß with a TeO2 exposure of 372.5 kg·yr and a median exclusion sensitivity to a 130Te 0vßß decay half-life of 1.7 · 1025 yr. We find no evidence for 0vßß decay and set a 90% C.I. (credibility interval) Bayesian lower limit of 3.2 · 1025 yr on the 130Te 0vßß decay half-life. In this work, we present the current status of CUORE's search for 0vßß, as well as review the detector performance. Finally, we give an update of the CUORE background model and the measurement of the 130Te two neutrino double-beta (2vßß) decay half-life.

SULPHATE is the dominant aerosol species in the Antarctic atmosphere1,2 and an important constituent in Antarctic snow and ice3. Various sources have been suggested for Antarctic non-sea-salt sulphate (n.s.s. SO2-4): volcanic emissions, stratospheric injection, pollutants transported from the low latitudes and biogenic dimethylsulphide (DMS) from the ocean1,2. Although the oceanic source is now believed to be especially important, there has been no strong chemical evidence directly linking oceanic DMS with the Antarctic n.s.s. SO2-4 concentrations. Here we present extended measurements from the Antarctic for both n.s.s. SO2-4 and methanesulphonate (MSA), an oxidation product of DMS. Both species have a very strong seasonal cycle with a maximum in the austral summer; this cycle parallels that of the oceanic biogenic sulphur producers, thereby suggesting a strong link between the Antarctic atmospheric sulphur cycle and biological processes in the Southern Ocean. © 1991 Nature Publishing Group.

Installation of water troughs is a common approach to increase densities of small game species in the Iberian peninsula but little is known about the watering patterns of target species, such as the wild rabbit (Oryctolagus cuniculus). Using camera trapping, we monitored the use of water troughs by wild rabbits over 228 weeks in three consecutive periods, from June to October in 2008, 2009 and 2010, on farmland in north–west Spain. Wild rabbits used 43% of the water troughs. A significantly higher number of rabbits were observed drinking at troughs surrounded by shrub cover than at those in open fields. Most drinking events were recorded from July to September (98%), though the use of water troughs was not clearly related to weather. Wild rabbits drank mainly during the morning (52% of rabbits), less so in the evening and at night, and rarely in the afternoon. Wild rabbits were photographed together with red–legged partridges (Alectoris rufa) in 6% of photographs. These findings suggest water troughs are useful for species such as wild rabbits and should be allocated close to shrub areas.