Metastability, negative specific heat and weak mixing in classical long-range many-rotator system

We perform a molecular dynamical study of the isolated $d=1$ classical Hamiltonian ${\cal H} = {1/2} \sum_{i=1}^N L_i^2 + \sum_{i \ne j} \frac{1-cos(\theta_i-\theta_j)}{r_{ij}^\alpha} ;(\alpha \ge 0)$, known to exhibit a second order phase transition, being disordered for $u \equiv U/N{\tilde N} \ge u_c(\alpha,d)$ and ordered otherwise ($U\equiv$ total energy and ${\tilde N} \equiv \frac{N^{1-\alpha/d}-\alpha/d}{1-\alpha/d}$). We focus on the nonextensive case $\alpha/d \le 1$ and observe that, for $u<u_c$, a basin of attraction exists for the initial conditions for which the system quickly relaxes onto a longstanding metastable state (whose duration presumably diverges with $N$ like ${\tilde N}$) which eventually crosses over to the microcanonical Boltzmann-Gibbs stable state. The temperature associated with the (scaled) average kinetic energy per particle is lower in the metastable state than in the stable one. It is exhibited for the first time that the appropriately scaled maximal Lyapunov exponent $\lambda_{u<u_c}^{max}(metastable) \propto N^{-\kappa_{metastable}} ;(N \to \infty)$, where, for all values of $\alpha/d$, $\kappa_{metastable}$ numerically coincides with {\it one third} of its value for $u>u_c$, hence decreases from 1/9 to zero when $\alpha/d$ increases from zero to unity, remaining zero thereafter. This new and simple {\it connection between anomalies above and below the critical point} reinforces the nonextensive universality scenario.Comment: 9 pages and 4 PS figure

Energetics of Radical Formation in Eumelanin Building Blocks: Implications for Understanding Photoprotection Mechanisms in Eumelanin

The supramolecular structure of melanin pigments is characterized by a high concentration of radical species. Therefore, the energetics of the radical formation in melanin building blocks is key for understanding the structure and the electronic properties of the pigments at the molecular level. Nevertheless, the radical energetics of even the simplest melanin building blocks are largely unknown. In order to address this fundamental issue, the bond dissociation enthalpies (BDEs) for the melanin monomers 5,6-dihydroxy-1<i>H</i>-indole-2-carboxylic acid (DHICA), 1<i>H</i>-indole-5,6-diol (DHI), and 1<i>H</i>-indole-5,6-dione (IQ) were determined through high-accuracy ab initio quantum chemistry methods. Our results provide strong evidence of the importance on BDEs for explaining the experimentally observed dependence of the antioxidant properties of eumelanin pigments on the DHICA/DHI ratio, and the role that these two species play on the photoprotection mechanism

Ionization of chlorophyll-c 2 in liquid methanol

a b s t r a c t The ionization of chlorophyll-c 2 in liquid methanol was investigated by a sequential quantum mechanical/Monte Carlo approach. Focus was placed on the determination of the first ionization energy of chlorophyll-c 2 . The results show that the first vertical ionization energy (IE) is red-shifted by 0.47 ± 0.24 eV relative to the gas-phase value. The red-shift of the chlorophyll-c 2 IE in the liquid phase can be explained by MgÁ Á ÁOH hydrogen bonding and long-ranged electrostatic interactions in solution. The ionization threshold for chlorophyll-c 2 in liquid methanol is close to 6 eV

Electronic properties of liquid hydrogen fluoride: A sequential quantum mechanical/Born-Oppenheimer molecular dynamics approach

The electronic properties of liquid hydrogen fluoride (HF) were investigated by carrying out sequential quantum mechanics/Born-Oppenheimer molecular dynamics. The structure of the liquid is in good agreement with recent experimental information. Emphasis was placed on the analysis of polarisation effects, dynamic polarisability and electronic excitations in liquid HF. Our results indicate an increase in liquid phase of the dipole moment (similar to 0.5 D) and isotropic polarisability (5%) relative to their gas-phase values. Our best estimate for the first vertical excitation energy in liquid HF indicates a blue-shift of 0.4 +/- 0.2 eV relative to that of the gas-phase monomer (10.4 eV). (C) 2010 Elsevier B.V. All rights reserved.Fundacao para a Ciencia e a Tecnologia (FCT), Portugal[PTDC/QUI/68226/2006]Fundacao para a Ciencia e a Tecnologia (FCT), Portuga

Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn-anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx-water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute-solvent electrostatic interaction. Our best estimate for the shift of the pi-pi* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of -2,520 +/- 90 cm(-1), which is only 110 cm(-1) (0.014 eV) below the experimental extrapolation of -2,410 +/- 90 cm(-1). This red-shift of around -2,500 cm(-1) can be divided in two distinct and opposite contributions. One contribution is related to the syn -&gt; anti conformational change leading to a blue-shift of similar to 1,700 cm(-1). Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around -4,200 cm(-1). Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.FCT (Portugal)CNPqCAPESFAPESPINCT-FCxnBioNet (Brazil

Electronic properties of liquid ammonia: A sequential molecular dynamics/quantum mechanics approach

The electronic properties of liquid ammonia are investigated by a sequential molecular dynamics/quantum mechanics approach. Quantum mechanics calculations for the liquid phase are based on a reparametrized hybrid exchange-correlation functional that reproduces the electronic properties of ammonia clusters [(NH(3))(n); n=1-5]. For these small clusters, electron binding energies based on Green's function or electron propagator theory, coupled cluster with single, double, and perturbative triple excitations, and density functional theory (DFT) are compared. Reparametrized DFT results for the dipole moment, electron binding energies, and electronic density of states of liquid ammonia are reported. The calculated average dipole moment of liquid ammonia (2.05 +/- 0.09 D) corresponds to an increase of 27% compared to the gas phase value and it is 0.23 D above a prediction based on a polarizable model of liquid ammonia [Deng , J. Chem. Phys. 100, 7590 (1994)]. Our estimate for the ionization potential of liquid ammonia is 9.74 +/- 0.73 eV, which is approximately 1.0 eV below the gas phase value for the isolated molecule. The theoretical vertical electron affinity of liquid ammonia is predicted as 0.16 +/- 0.22 eV, in good agreement with the experimental result for the location of the bottom of the conduction band (-V(0)=0.2 eV). Vertical ionization potentials and electron affinities correlate with the total dipole moment of ammonia aggregates. (c) 2008 American Institute of Physics

Ionization of chlorophyll-c(2) in liquid methanol

The ionization of chlorophyll-c(2) in liquid methanol was investigated by a sequential quantum mechanical/Monte Carlo approach. Focus was placed on the determination of the first ionization energy of chlorophyll-c(2). The results show that the first vertical ionization energy (IE) is red-shifted by 0.47 +/- 0.24 eV relative to the gas-phase value. The red-shift of the chlorophyll-c(2) IE in the liquid phase can be explained by Mg center dot center dot center dot OH hydrogen bonding and long-ranged electrostatic interactions in solution. The ionization threshold for chlorophyll-c2 in liquid methanol is close to 6 eV. (C) 2012 Elsevier B.V. All rights reserved.FCT (Portugal)CNPqCAPESFAPESPINCTFCxnBioNet (Brazil