Biomedical subjects

László Turi

Publications and source records attributed to László Turi.

4 recordsLinked to original sources

PubMed2006

Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: application to solvated electrons in water and methanol.

A new, alternative form of the golden rule formula defining the nonadiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the nonadiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via molecular dynamics simulations. The formalism is applied to the problem of the nonadiabatic p-->s relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvents, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated nonadiabatic coupling.

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PubMed2006

Excess electron localization sites in neutral water clusters.

We present approximate pseudopotential quantum-mechanical calculations of the excess electron states of equilibrated neutral water clusters sampled by classical molecular dynamics simulations. The internal energy of the clusters are representative of those present at temperatures of 200 and 300 K. Correlated electronic structure calculations are used to validate the pseudopotential for this purpose. We find that the neutral clusters support localized, bound excess electron ground states in about 50% of the configurations for the smallest cluster size studied (n = 20), and in almost all configurations for larger clusters (n > 66). The state is always exterior to the molecular frame, forming typically a diffuse surface state. Both cluster size and temperature dependence of energetic and structural properties of the clusters and the electron distribution are explored. We show that the stabilization of the electron is strongly correlated with the preexisting instantaneous dipole moment of the neutral clusters, and its ground state energy is reflected in the electronic radius. The findings are consistent with electron attachment via an initial surface state. The hypothetical spectral dynamics following such attachment is also discussed.

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PubMed2005

Characterization of excess electrons in water-cluster anions by quantum simulations.

Water-cluster anions can serve as a bridge to understand the transition from gaseous species to the bulk hydrated electron. However, debate continues regarding how the excess electron is bound in (H2O)-n, as an interior, bulklike, or surface electronic state. To address the uncertainty, the properties of (H2O)-n clusters with 20 to 200 water molecules have been evaluated by mixed quantum-classical simulations. The theory reproduces every observed energetic, spectral, and structural trend with cluster size that is seen in experimental photoelectron and optical absorption spectra. More important, surface states and interior states each manifest a characteristic signature in the simulation data. The results strongly support assignment of surface-bound electronic states to the water-cluster anions in published experimental studies thus far.

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PubMed2004

Critical evaluation of approximate quantum decoherence rates for an electronic transition in methanol solution.

We present a quantum molecular dynamics calculation of a semiclassical decoherence function to evaluate the accuracy of alternative short-time approximations for coherence loss in the dynamics of condensed phase electronically nonadiabatic processes. The semiclassical function from mixed quantum-classical molecular dynamics simulations and frozen Gaussian wave packets is computed for the electronic transition of an excited state excess electron to the ground state in liquid methanol. The decoherence function decays on a 10 fs time scale that is qualitatively similar to the aqueous case. We demonstrate that it is the motion of the hydrogen atom, and, in particular, the hydrogen rotation around the oxygen-methyl bond which is predominantly responsible for destroying the quantum correlations between alternative states. Multiple time scales due to the slower diffusive nuclear modes, which dominate the solvation response of methanol, do not contribute to the coherence loss. The choice of the coordinate representation is investigated in detail and concluded to be irrelevant to the decay. Changes in both nuclear momenta and positions on the two alternative potential surfaces are found to contribute to decoherence, the former dominating at short times (t < 5 fs), the latter controlling the decay at longer times. Various short-time approximations to the full dynamics for the decoherence function are tested for the first time. The present treatment rigorously develops the short-time description and establishes its range of validity. Whereas the lowest-order short-time approximation proves to be a very good approximation up to about 5 fs, we also find that it bounds the decay of the decoherence function. After 5 fs, the coherence decay in fact becomes faster than the single Gaussian predicted in the lowest-order short-time limit. This decay is well reflected by an enhanced low-order approximation, which is also easily computed from equilibrium classical forces.

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