Biomedical subjects

Lorenz S Cederbaum

Publications and source records attributed to Lorenz S Cederbaum.

At least 19 recordsLinked to original sources

PubMed2006

Ionization and double ionization of small water clusters.

The valence ionization and double ionization spectra of the water molecule, of the water dimer, and the cyclic water clusters (H2O)3 and (H2O)4 are calculated by ab initio Green's function methods and discussed in some detail. Particular attention is paid to the analysis of the development of the spectra with increasing cluster size. Electronic decay following inner valence ionization is addressed and a crude estimate for the kinetic energy spectrum of the secondary electrons is given for the clusters.

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PubMed2006

Combined experimental-theoretical study of the lower excited singlet states of paravinyl phenol, an analog of the paracoumaric acid chromophore.

The low-lying excited singlet states of paravinyl phenol (pVP) are investigated experimentally and theoretically paying attention to their similarity to excited states of paracoumaric acid, the chromophore of the photoactive yellow protein (PYP). Resonance enhanced multiphoton ionization and laser induced fluorescence spectroscopic techniques are employed to obtain supersonically cooled, vibrationally resolved excitation and emission spectra related to the lowest (1)A'(V') excited state of pVP. Comprehensive analyses of the spectral structures are carried out by means of the equation-of-motion coupled cluster singles and doubles and time dependent density functional theory methods in combination with the linear vibronic coupling model and Franck-Condon calculations. The assignments of the spectral patterns are given, mostly in terms of excitations of totally symmetric modes. Weak activity of the non-totally-symmetric modes indicates low probability of photochemical processes in the Franck-Condon region of the (1)A'(V') state. The second (1)A'(V) and third (1)A" (Ryd) excited states of pVP are characterized with regard to their electronic structure, properties, and effects of geometry relaxations. The lengthening of the double bond relevant to the trans-cis isomerization of the PYP chromophore is found for the (1)A'(V) state. A possibility of photochemical processes and strong vibronic interactions in this state can be expected. The theoretical results for the (1)A"(Ryd) state predict that dissociation with respect to the O-H bond is possible.

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PubMed2006

Calculation of interatomic decay widths of vacancy states delocalized due to inversion symmetry.

In a recent publication [J. Chem. Phys. 123, 204107 (2005)], we have introduced a new ab initio approach for the calculation of the widths of interatomic electronic decay of inner-shell vacancies in clusters. The new technique is based on the configuration interaction formalism first introduced for the description of resonance states by Fano [Phys. Rev. 124, 1866 (1961)] and on a Green function method for the description of the many-electron states involved in the electronic decay. Central to the new method is the selection of the physical excitation operators for the construction of the initial and final states of the interatomic decay. The previously described selection procedure has been formulated for localized vacancy states and runs into difficulties when applied to the decay of vacancy states delocalized due to inversion symmetry, e.g., (2s(-1)) 2Sigma(g,u)+ states of Ne2+. Here we present a modified computational scheme suitable for interatomic decay of the energy-split gerade and ungerade states and apply it to the interatomic Coulombic decay in two homonuclear diatomic clusters: Ne2 and Ca2.

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PubMed2006

Ionization spectra and electronic decay in small iodide clusters: fully relativistic results.

Singly ionized systems in high-lying energetic final states can stabilize themselves via various electronic decay mechanisms. With increasing system size interatomic and intermolecular processes dominate over intra-atomic (Auger) decay channels. For the small (HI)(2) and (LiI)(2) clusters fully relativistic ionization spectra are calculated and the subsequent electronic decay of the cations is investigated. Due to the presence of the iodine atom a fully relativistic description is mandatory and was performed by the algebraic diagrammatic construction technique in its four-component form. The lifetimes of the singly ionized final states are estimated by the application of Weisskopf-Wigner [Z. Phys. 63, 54 (1930)] theory.

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PubMed2006

Interatomic Coulombic decay in a heteroatomic rare gas cluster.

Interatomic decay in a heteroatomic rare gas cluster (NeAr) is studied in detail using ab initio electronic structure description and nuclear dynamics simulations. Decay widths of all possible interatomic decay processes are calculated by the recently developed method based on Green's function formalism. Kinetic energy spectra of the electrons emitted in the course of interatomic Coulombic decay (ICD) are simulated for a series of initial vibrational states of the neutral cluster. The effect of the nuclear dynamics on the ICD electron spectra is discussed.

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PubMed2006

Short-time dynamics through conical intersections in macrosystems. I. Theory: effective-mode formulation.

The short-time dynamics through a conical intersection of a macrosystem comprising a large number of nuclear degrees of freedom (modes) is investigated. The macrosystem is decomposed into a "system" part carrying a limited number of modes, and an "environment" part. An orthogonal transformation in the environment's space is introduced, as a result of which a subset of three effective modes can be identified which couple directly to the electronic subsystem. Together with the system's modes, these govern the short-time dynamics of the overall macrosystem. The remaining environmental modes couple, in turn, to the effective modes and become relevant at longer times. In this paper, we present the derivation of the effective Hamiltonian, first introduced by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)], and analyze its properties in some detail. Several special cases and topological aspects are discussed.

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PubMed2006

Short-time dynamics through conical intersections in macrosystems. II. Applications.

We present several numerical applications based upon the effective-mode formulation for the short-time dynamics through conical intersections in macrosystems, as detailed in the preceding paper and first proposed by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)]. The macrosystem, containing a vast number of nuclear degrees of freedom (modes), is decomposed into a system part and an environment part. Only three effective environmental modes are needed-together with the system's modes-to accurately calculate the low resolution spectra and the short-time dynamics of the entire macrosystem. For the systems discussed here, results are compared to those of a full quantum wave-packet propagation. Some rules are extracted to provide general tendencies; these rules allow one to understand and predict the dynamical properties in more general situations where the exact quantum dynamics of the macrosystem is out of reach.

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PubMed2006

Interatomic decay of inner-valence-excited states in clusters.

In an isolated atom, excitation of an inner valence electron above the outer valence subshell leads to creation of an autoionizing state. Recently, it has been demonstrated experimentally that in a cluster, the inner-valence-excited states can decay also by an interatomic mechanism which has been called resonant interatomic Coulombic decay (RICD). Here we show that RICD is indeed the leading but not the only possible interatomic decay mode of the inner-valence excitations in clusters. Using Ne (2s-->3p) excitation in MgNe cluster as an example, we explore the possible decay mechanisms and draw conclusions on their relative importance and on the nature of the corresponding decay products.

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PubMed2006

Interatomic electronic decay in endohedral fullerenes.

Ionization of an atom in an endohedral fullerene complex can lead to a wealth of nonradiative decay processes. These interatomic processes occur due to the correlation existing between the atomic and the fullerene electrons and do not take place in the free species . Considering as an example, we calculate the rates of the interatomic decay processes and show that the interatomic decay in is ultrafast. Moreover, our analysis suggests that interatomic decay in an endohedral fullerene does not necessarily lead to the destruction of the complex.

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PubMed2006

A small and stable covalently bound trianion.

Stable doubly charged anions have become well known over the past decade, but the knowledge about higher-charged molecules is still sparse. Especially the minimum size of a covalently bound trianion which is still stable is an open question. Here, we present the smallest trianion of this kind known up to now, namely, B(C(2)CO(2))(3) (3-). After establishing its geometrical parameters, we investigate its stability with respect to electron autodetachment and fragmentation of the molecular framework. Our results lend strong support to the notion that this trianion indeed represents a stable compound which should be observable in the gas phase.

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PubMed2005

Stable and long-lived trianions in the gas phase.

Stable doubly charged anions have become well known over the past decade, but the knowledge about higher charged molecules is still sparse. In this article, we discuss the current status of trianions. The different species, both from experimental and theoretical work, are classified according to their bonding characteristics, that is, ionic, metallic, or covalent. Both stability with respect to electron autodetachment and with respect to dissociation is covered. New results on the currently smallest stable covalently bound trianion are also shown. Last, we outline future perspectives in the field of multiply charged anions.

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PubMed2005

Simulation of a complex spectrum: interplay of five electronic states and 21 vibrational degrees of freedom in C5H4 +.

Using a five-state, all-mode vibronic coupling model Hamiltonian derived in a previous publication [A. Markmann et al., J. Chem. Phys. 122, 144320 (2005)], we have calculated the photoelectron spectrum of the pentatetraene cation in the neighborhood of the B (2)E state, which can be represented with charge-localized components. To this end, quantum nuclear dynamics calculations were performed using the multiconfiguration time-dependent Hartree method, taking all 21 vibrational normal modes into account. Compared to experiment, the main features are reproduced but higher accuracy experiments are necessary to gauge the accuracy of the predictions for the vibronic progressions at the rising flank of the spectrum.

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PubMed2005

Ab initio calculation of interatomic decay rates by a combination of the Fano ansatz, Green's-function methods, and the Stieltjes imaging technique.

A new computational technique is introduced for the ab initio calculation of the rates of interatomic and intermolecular nonradiative decay processes occurring due to electronic correlation. These recently discovered phenomena are described theoretically using the configuration-interaction formalism first introduced by Fano [Phys. Rev. 124, 1866 (1961)] and later adapted to an Auger decay by Howat et al. [J. Phys. B 11, 1575 (1978)]. The boundlike and the continuumlike components of the wave function of the decaying state are constructed using a Green's-function method known as algebraic diagrammatic construction. A combination of atomic and distributed Gaussian basis sets is shown to provide an adequate description of both boundlike and continuumlike wave-function components. The problem of the normalization of the continuum (final state) wave function is addressed using the Stieltjes imaging technique. The new method is applied to the calculation of the rates of interatomic decay in alkaline-earth-rare-gas clusters. The obtained results help to verify our earlier conclusions [Phys. Rev. Lett. 93, 263002 (2004)] regarding the validity of the virtual-photon transfer model for the interatomic Coulombic decay. In addition, we demonstrate that the process of electron-transfer-mediated decay is responsible for the finite lifetimes of the outer valence vacancies in alkaline-earth-rare-gas clusters.

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PubMed2005

Competitive charge- and energy-transfer processes following core ionization in the Na- CO cluster.

Anion-molecule clusters constitute a very suitable class of systems for studying intermolecular (interatomic) charge-transfer (CT) processes following core ionization. A weakly bound electron of the anion in these clusters can be easily transferred to the core-ionized molecule. The screening effect of this electron may have a dramatic impact on core-level spectra and even account for a breakdown of the quasiparticle picture of core ionization. This is demonstrated here by calculating the O1s(-1) and C1s(-1) core ionization spectra of the Na- CO cluster using an ab initio fourth-order Green's-function method. Interestingly, along with the CT processes in this cluster there exist also very efficient energy-transfer (ET) processes favored by the low excitation energies of Na-. These ET processes constitute an appreciable part of the electronic excitations following core ionization of Na- CO and exert thereby a strong influence on the spectra studied. The spectral features attributed to the ET processes are as pronounced as those attributed to the CT processes. Major differences in the behavior of CT and ET satellites as a function of the anion-molecule separation are found and explained. We compare also the O1s(-1) core ionization spectra of the Na- CO and Na- H2O clusters. Along with a certain similarity, these spectra exhibit substantial differences which are essentially attributed to the distinct cluster geometries.

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PubMed2005

Pathway from condensation via fragmentation to fermionization of cold bosonic systems.

For small scattering lengths, cold bosonic atoms form a condensate the density profile of which is smooth. With increasing scattering length, the density gradually acquires more and more oscillations. Finally, the number of oscillations equals the number of bosons and the system becomes fermionized. On this pathway from condensation to fermionization intriguing phenomena occur, depending on the shape of the trap. These include macroscopic fragmentation and coexistence of condensed and fermionized parts that are separated in space.

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PubMed2005

Quantum states of magnetically induced anions.

In a magnetic field, an atom (or molecule) can attach an extra electron to form an unconventional anionic state which has no counterparts in field-free space. Assuming the atom to be infinitely heavy, these magnetically induced anionic states are known to constitute an infinite manifold of bound states. In reality, the species can move and its motion across the magnetic field couples to the motion of the attached electron. We treat this coupling, for the first time, quantum mechanically, and show that it makes the number of bound anionic states finite. Explicit numerical quantum results are presented and discussed.

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PubMed2005

Multielectron wave-packet propagation: general theory and application.

An ab initio method for multielectron wave-packet propagation in relatively large systems is presented. It allows the description of ultrafast electron dynamics processes before the coupling with the nuclear motion becomes important. The method is applied to the amino acid glycine for the investigation of the migration of hole charge following the ionization of the system. Two different mechanisms of ultrafast charge migration are identified and discussed. It is shown that the electron correlation can be the driving force for the charge-transfer dynamics in glycine.

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PubMed2005

Zoo of quantum phases and excitations of cold bosonic atoms in optical lattices.

Quantum phases and phase transitions of weakly to strongly interacting bosonic atoms in deep to shallow optical lattices are described by a single multiorbital mean-field approach in real space. For weakly interacting bosons in one dimension, the critical value of the superfluid to Mott insulator (MI) transition found is in excellent agreement with many-body treatments of the Bose-Hubbard model. For strongly interacting bosons, (i) additional MI phases appear, for which two (or more) atoms residing in each site undergo a Tonks-Girardeau-like transition and localize, and (ii) on-site excitation becomes the excitation lowest in energy. Experimental implications are discussed.

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