Ab initio study for structure, electric properties and light emission of linear-trans-quinacridone

The structure, electric properties and emission rate of linear-trans-quinacridone are investigated within the density functional theory (DFT) calculations. We find the structure of the molecule to be planar with an energy gap of 3.06 eV. The emission lifetime from the lowest unoccupied molecular orbital (LUMO) to the highest occupied molecular orbital (HOMO) of this material is found to be 24 ns, which is in good agreement with experimental results.     

Selective preparation of ground state wave-packets: a theoretical analysis of femtosecond pump-dump-probe experiments on the potassium dimer

We present simulations on pump-dump-probe experiments performed on the potassium dimer. The interaction of two time-delayed laser pulses prepares vibrational wave packets in the electronic ground state. The quantum calculations reveal to what extent it is possible to prepare a ground state superposition of states with high versus low vibrational quantum numbers by changing the pump-dump delay time. It is shown that transient signals may exhibit interference effects which are due to characteristics of ground state wave-packets composed of two components showing different vibrational dynamics. In this way the signals are able to yield information about vibrational overtone motion. Received 27 September 2000 and Received in final form 21 November 2000     

Femtosecond pump-probe fluorescence signals from classical trajectories: comparison with wave-packet calculations

A classical approach to simulate femtosecond pump-probe experiments is presented and compared to the quantum mechanical treatment. We restrict the study to gas-phase systems using the I₂ molecule as a numerical example. Thus, no relaxation processes are included. This allows for a direct comparison between purely quantum mechanical results and those obtained from classical trajectory calculations. The classical theory is derived from the phase-space representation of quantum mechanics. Various approximate quantum mechanical treatments are compared to their classical counterparts. Thereby it is demonstrated that the representation of the radial density as prepared in the pump-process is most crucial to obtain reliable signals within the classical approach. Received 28 March 2001     

Quantum chemical construction of a reduced reaction Hamiltonian and T 1 -relaxation and pure T 2 -dephasing rates for the proton transfer in 3-chlorotropolone

Separating multidimensional problems into that of a relevant system which is coupled to a bath of harmonic oscillators is a common concept in condensed phase theory. Focusing on the specific problem of intramolecular proton transfer in an isolated tropolone derivative, we consider the reactive proton moving in the plane of the molecule as the system and the remaining substrate normal modes as the bath. An all-Cartesian system-plus-substrate Hamiltonian is constructed employing density functional theory. It is then used to determine the temperature-dependent effective reduced reaction Hamiltonian and the state-to-state dissipation rates induced via the system-substrate coupling up to the bi-quadratic order. The important substrate modes for the T₁-relaxation and the pure T₂-dephasing rates, which are either intra- or inter-well in nature, are identified numerically and analyzed physically with molecular details. Received 19 November 2001 and Received in final form 19 February 2002     

Quantum Brownian motion on potential surfaces coupled via tunneling in an external electric field[-2mm]

The present paper deals with the motion of a Brownian particle on two identical but shifted potential surfaces, coupled via a tunneling matrix element in an external electric field. Dissipation is induced by a heat bath represented by an infinite set of harmonic oscillators with a continuum range of frequencies. We derive a perturbative solution for the quantum coherence term of the particle system after performing a small-polaron-like transformation. This is subsequently necessary for the extraction of an equation that describes the reduced dynamics and the minimal action path of the Brownian particle. Finally we extract expressions for the population relaxation rate and the pure quantum-dephasing rate of the two-level system. Received 4 January 2001 and Received in final form 12 March 2001     

Non-Markovian relaxation in an open quantum system

Non-Markovian dynamics in open quantum systems is characterized by a time-non-locality in the equation of motion valid for the reduced density operator. An expansion of this density matrix equation with respect to Laguerre polynomials is used to tackle the time-non-locality. The applicability and the numerical limitations of the method are discussed in detail. In order to illuminate the characteristics of non-Markovian dynamics the reference example is studied of a single quantum degree of freedom moving in a harmonic potential and being embedded in a heat bath. If interpreted as the photoinduced dynamics of nuclear motion in polyatomic molecules we can suggest two clear signatures of non-Markovian dynamics observable in ultrafast optical experiments, firstly a pronounced and somewhat irregular oscillatory behavior of the vibrational level populations, and secondly a separation of the vibrational wavepacket into a double-structure. Received 12 April 2000 and Received in final form 2 September 2000     

Nature of quantum recurrences in coupled higher dimensional systems

We investigate recurrence phenomena in coupled two degrees of freedom systems. It is shown that an initial well localized wave packet displays recurrences even in the presence of coupling in these systems. We discuss the interdependence of time scales namely classical period and quantum revival time and explain the significance of initial conditions.     

Large parity violating effects in atomic dysprosium with nearly degenerate Floquet eigenvalues

In this article we study effects of parity nonconservation in atomic dysprosium, where one has a pair of nearly degenerate levels of opposite parity. We consider the time evolution of this two-level system within oscillatory electric and magnetic fields. These are chosen to have a periodical structure with the same period, such that a Floquet matrix describes the time evolution of the quantum states. We show that, if the states are unstable, the eigenvalues of the Floquet matrix may have contributions proportional to the square root of the parity violating interaction matrix element while they are almost degenerate in their parity even part. This leads to beat frequencies proportional to which are expected to be larger by several orders of magnitude compared to ordinary P-violating contributions which are of order . However, for the simple field configurations we considered, it still seems to be difficult to observe these P-violating beat effects, since the states decay too fast. On the other hand, we found that, within only a few Floquet cycles, very large parity violating asymmetries with respect to experimental setups of opposite chirality may be obtained. The electric and magnetic fields as well as the time intervals necessary for this are in an experimentally accessible range. For statistically significant effects beyond one standard deviation a number of about 10⁷ atoms is required. Our ideas may be applied directly to other 2-level atomic systems and different field configurations. We hope that these ideas will stimulate experimental work in this direction. Received 16 September 1999 and Received in final form 10 March 2000     

Metastable states,the adiabatic theorem and parity violating geometric phases I

A system of metastable plus unstable states is discussed. The mass matrix governing the time development of the system is supposed to vary slowly with time. The adiabatic limit for this case is studied and it is shown that only the metastable states obtain the analogs of the dynamical and geometrical phase factors familiar from stable states. Abelian and non-Abelian geometric phase factors for metastable states are defined.     

Metastable states,the adiabatic theorem and parity violating geometric phases II

We discuss and calculate parity conserving (PC) and parity violating (PV) geometric phases for the metastable 2S states of hydrogen and deuterium. The atoms are supposed to be subjected to slowly varying electric and magnetic fields which act as external parameters for the atoms. Geometric flux density fields are introduced which allow for an easy overview how to choose the paths in parameter space in order to obtain only PC or only PV geometric phases. The PV phases are calculated in the Standard Model of particle physics. Even if numerically they come out small they have interest of principle as a new manifestation of parity violation in atomic physics. Electronic supplementary material Supplementary Online Material     

Analysis and control of ultrafast photodissociation processes in organometallic molecules

In this paper we characterize the ultrafast fragmentation in electronically excited Fe(CO)₂(NO)₂ and CpMn(CO)₃ by means of femtosecond time-resolved spectroscopy combined with mass spectrometry. From the transient two-color multi-photon ionization data, it was possible to record the transients of the parent molecule ions and their photofragment ions. The experimentally observed decay times indicated an ultrafast loss of the first ligands (sub-100 fs decay times). Further we performed a feedback control experiment on the photofragmenting CpMn(CO)₃ molecular system in order to maximize the yield of desired ionic products through pulse modulation. The shape of the pulses obtained from optimization reflect well the intrinsic molecular dynamics during photofragmentation and the change of the CpMn(CO)⁺/CpMn(CO)₃ ⁺ ratio shows a clear evidence for the capability of the optimization method to find tailor-made system-specific pulses. Received 9 January 2001     

Jaynes-Cummings-model with damping at resonance

The time evolution of a damped two-level atom coupled to a damped field mode at resonance is calculated analytically as well as numerically in the basis of dressed states. We study the dynamics of the density matrix and of observables, e.g. the number of field quanta. For the initial states we consider the field to be in a Fock or Glauber state and the atom in the ground or excited state. We show the significant influence of the damping on the well-known phenomena of this model, e.g. collapse and revival. Received 22 January 2001 and Received in final form 16 May 2001     

Parity violation in hydrogen and longitudinal atomic beam spin echo I

We discuss the propagation of hydrogen atoms in static electric and magnetic fields in a longitudinal atomic beam spin echo (lABSE) apparatus. There the atoms acquire geometric (Berry) phases that exhibit a new manifestation of parity-(P-)violation in atomic physics. We provide analytical as well as numerical calculations of the behaviour of the metastable 2S states of hydrogen. The conditions for electromagnetic field configurations that allow for adiabatic evolution of the relevant atomic states are investigated. Our results provide the theoretical basis for the discussion of possible measurements of P-violating geometric phases in lABSE experiments.     

Micelles of poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) terpolymers in aqueous media and their interaction with surfactants

Well-defined poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) (PI-P2VP-PEO) triblock terpolymers were synthesized by anionic polymerization high-vacuum techniques. The terpolymers formed spherical three-layer (onion-type) micelles in neutral and acidic pH aqueous media as evidenced by static and dynamic light scattering. In pure water, kinetically frozen micelles with a core composed of a soft PI inner part and a hard P2VP outer shell and protected by a neutral PEO corona were formed. In acidic media the core was formed by the soft PI hydrophobic segment, whereas the corona consisted of an inner cationic polyelectrolyte P2VPH⁺ part and an outer PEO shell. The aggregation numbers were found to be high in all cases, due to the high hydrophobicity of the core-forming blocks. In the latter case an increase in size was observed due to the electrostatic repulsions between the P2VPH⁺ chains in the inner part of the corona, which is also responsible for the lower aggregation numbers observed in the acidic solutions. The interaction of these onion-type micelles with cationic (DTMAB) and anionic (SDS) surfactants led to the formation of mixed polymer/surfactant aggregates. Their structural characteristics could be varied by combining changes in surfactant type and concentration, solution pH and type of electrostatic interaction, leading to interesting, block-copolymer-based, environmentally responsive colloidal systems.     

Molecular dynamics of laser-assisted decomposition of unstable molecules at the surface of carbon nanotubes: case study of CH2(NO2)2 on CNT(4,0)

ABSTRACT

In this study, photoreactions of the dinitromethane molecule noncovalently adsorbed on the (4, 0) carbon nanotube (CNT) have been investigated by time-dependent, excited-state molecular dynamics, which takes into account simultaneous evolution of electronic excitation and nuclear positions under periodic optical excitations. It is found that desorption of molecular adsorbate from CNT surface can be controlled by UV?vis photoexcitations. In addition, it is shown that the presence of CNT substrate facilitates photodecomposition of the adsorbate molecule, related to optically controlled explosion. This model demonstrates potential of photoinduced charge transfer between the adsorbate and substrate, which can affect efficiency of desorption and decomposition reactions. This process has a potential use as a remote trigger for larger scale detonations, or as a mechanism for ‘cleaning’ CNTs of unwanted functionalisation.     

Dynamics of isolated twin boundary in (TMTSF)

Intermittent and irregular motion of isolated twin boundary (kink) in organic crystal (TMTSF)₂PF₆ was studied at room temperature. Both the local velocity and the time of intermission are determined not only by external stress and temperature but also by the time (t w) elapsed after the backward passage and before the following forward one. When the kink moves after longer t w, its velocity becomes smaller and the time of intermission longer. Both tend to saturate for t w longer than 10² s. This result indicates that some disorder is induced in the lattice by the backward motion and it is relaxed during t w. We also found that the effect of the backward motion of one kink on its following motion is equivalent quantitatively to that of the forward motion of the pair-created counterpart. Received: 14 April 1998 / Received in final form and Accepted: 1st September 1998     

Violet-blue-shift of emission and enhanced luminescent properties of Ca3(PO4)2:Ce3+ phosphor induced by substitution of Gd3+ ions

Ca₃(PO₄)₂:1mol%Ce³⁺/xGd³⁺ (where x = 0.5, 1.0, 3.0 and 5.0 mol%) phosphors were synthesized by the conventional combustion synthesis method. The X-ray diffraction patterns showed their rhombohedral structure with space group of R3c. The optical properties including reflectance, excitation and emission were investigated. The band gaps of the phosphors were calculated from diffuse reflectance spectra data using the Kubelka–Munk function. The photoluminescence (PL) excitation spectra exhibited the broadband 4f–5d transition of Ce³⁺ ions centered at ~265 nm. The PL emission properties of the Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphors were studied as a function of the Gd³⁺ ion concentration. The Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphor had a wide emission band ranging from 320 to 400 nm, and peaking at 365 nm. This emission is ascribed to the transition from the higher 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. The 365 nm peak shifted to longer wavelengths with increasing concentration of the Gd³⁺ ion. The CIE chromaticity diagram of Ca₃(PO₄)₂:Ce³⁺/Gd³⁺ phosphor showed tunable emission colour from violet to violet-blue, suggesting that this phosphor can act as a source of violet-blue colour for application in information displays, phototherapy and photoluminescent liquid crystal displays.     

A Raman spectroscopic study of copiapites Fe2+Fe3+(SO4)6(OH)2 · 20H2O: environmental implications

Raman spectroscopy has been used to study selected mineral samples of the copiapite group. Copiapite (Fe²⁺Fe³⁺(SO₄)₆(OH)₂ · 20H₂O) is a secondary mineral formed through the oxidation of pyrite. Minerals of the copiapite group have the general formula AFe₄(SO₄)₆(OH)₂ · 20H₂O, where A has a + 2 charge and can be either magnesium, iron, copper, calcium and/or zinc. The formula can also be B_2/3Fe₄(SO₄)₆(OH)₂ · 20H₂O, where B has a + 3 charge and may be either aluminium or iron. For each mineral, two Raman bands are observed at around 992 and 1029 cm⁻¹, assigned to the (SO₄)²⁻ν₁ symmetric stretching mode. The observation of two bands provides evidence for the existence of two non‐equivalent sulfate anions in the mineral structure. Three Raman bands at 1112, 1142 and 1161 cm⁻¹ are observed in the Raman spectrum of copiapites, indicating a reduction of symmetry of the sulfate anion in the copiapite structure. This reduction in symmetry is supported by multiple bands in the ν₂ and ν₄(SO₄)²⁻ spectral regions. Copyright © 2010 John Wiley & Sons, Ltd.