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  • Articles  (103)
  • American Chemical Society (ACS)  (90)
  • American Institute of Physics (AIP)  (13)
  • Chemistry and Pharmacology  (103)
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  • Articles  (103)
  • 1
    Publication Date: 2016-07-29
    Description: Colloidal particles were exposed to a random potential energy landscape that has been created optically via a speckle pattern. The mean particle density as well as the potential roughness, i.e., the disorder strength, were varied. The local probability density of the particles as well as its main characteristics were determined. For the first time, the disorder-averaged pair density correlation function g (1) ( r ) and an analogue of the Edwards-Anderson order parameter g (2) ( r ), which quantifies the correlation of the mean local density among disorder realisations, were measured experimentally and shown to be consistent with replica liquid state theory results.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 6031-6051 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rotational motion of homonuclear diatomic molecules confined to two dimensions at finite temperatures is discussed within the framework of path-integral Monte Carlo (PIMC) techniques. For single rotators the symmetry restriction on the total wave function coupling nuclear spin and rotations of these diatomic molecules is carried over to PIMC for fermionic and bosonic diatomic molecules. Three experimentally relevant quantum statistical averages are formulated, and quantum effects due to discrete level spacing and exchange are separated with the help of these averages. The method is applied to single N2 and H2 rotators adsorbed on graphite in the frozen-in crystal field which is due to the commensurate ((square root of)3×(square root of)3)R30° "2-in'' herringbone phase. Contrary to H2, exchange effects are negligible for N2 in the relevant temperature range. The resulting sign problem for certain combinations of molecule and averaging procedure is discussed. PIMC simulations of the phase transition from the translationally (square root of)3-ordered and orientationally disordered phase to the herringbone phase were carried out for complete N2 monolayers without a symmetry restriction on the wave function. Due to dispersive quantum fluctuations, transition temperature and ground-state order parameter are depressed by roughly 10% as compared to classical MC simulations of the same realistic model. In addition, the PIMC results are compared to quasiharmonic and quasiclassical approximations. The quasiharmonic treatment yields the correct order parameter suppression, the quasiclassical simulation the lowering of the transition temperature, but only the full quantum PIMC simulations describe the entire temperature range of interest correctly.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 4193-4202 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A theoretical treatment is presented that demonstrates universal dynamical behavior in the isotropic phase of liquid crystals on ultrafast time scales and short distance scales. The theoretical development generates a temperature independent power law for the short time scale decay of the molecular orientational correlation function. This provides a theoretical rationale for the postulate of universal behavior based on recent experimental observations on two liquid crystal systems. A temperature independent power law decay with the identical exponent, 0.63, was observed for the two systems. First, an alternative theoretical approach reproduces the Landau de Gennes results for the long distance scale, slow time scale orientational dynamics in the isotropic phase. This approach is also capable of examining the short distance scale and short time scale dynamics, and yields a temperature independent power law decay with exponent 0.5. Then critical correlations of fluctuations and local symmetry considerations are included. The Ising model of critical systems is employed. This detailed analysis yields the experimentally observed exponent, 0.63, without recourse to adjustable parameters. Modern theories of dynamic critical phenomena like dynamic scaling theory, the kinetic Ising model and the stochastic model of Karder–Parisi–Zhang are considered as alternative approaches. While these theories can generate some of the features found in experiment, it is not possible to reproduce the observed experimental results without internal inconsistencies or unwarranted adjustable parameters. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The minimum energy potential energy surfaces for combination of NH(3Σ−)+O(3P) to form HNO(1A',3A‘) and N(4S)+OH(2Π) to form NOH(3A‘), and the isomerization of HNO(1A',3A‘) to NOH(1A',3A‘), decomposition of NOH(1A',3A‘) to N(4S)+OH(2Π) as well as to H(2S)+NO(2Π) and HNO(3A‘) to H(2S)+NO(2Π) have been obtained by the ab initio methods with geometry optimization at the 6–311G**/MP2=full level with corrections for electron correlation at the MP4SDTQ=full level. At all stationary points on the potential energy surfaces (PES), correction for the zero point vibrational energies are made. The addition reactions to form energized adducts have then been analyzed using a bimolecular version of the quantum statistical Rice–Ramsperger–Kassel (QRRK) theory at different temperatures and pressures. Our analysis predicts that at all temperatures isomerization of HNO(3A‘) to NOH(3A‘) and its reverse isomerization are important. Formation of NO(2Π) in the interstellar clouds can take place from decomposition of NOH(3A‘) as well as HNO(3A‘).
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 1673-1683 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The orientational dynamics of phenyl side groups in poly(methylphenylsiloxane) (PMPS) melts are examined over a broad range of viscosity/temperature (η/T) using subpicosecond transient grating optical Kerr effect (TGOKE) measurements. Measurements on poly(dimethylsiloxane) are also reported. Following ultrafast (hundreds) of fs librational dynamics, the phenyl side group orientational dynamics occur over a range of times from 2 ps to a few hundred ps. The experiments were performed from 25 to 143 °C, resulting in η/T changing by a factor of 40. In spite of the large change in η/T, the side group dynamics remain unchanged throughout the entire temperature range. Comparison of the dynamics of PMPS in the melt and PMPS in dilute CCl4 solution shows that chain–chain interactions influence the phenyl side group dynamics in the melt. The dynamics are described as local orientational relaxation of phenyl groups in the microenvironments defined by the backbone geometry and side group steric interactions rather than rotational diffusion. The dynamics exhibit power-law behavior, t−α, over two decades of signal decay. Two possible physical processes that can give rise to a power-law decay are discussed. The relationship of the observed dynamics to the β and α relaxations of glass forming liquids is also discussed.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 9888-9896 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electronic couplings in long-range electron transfer have been calculated using ab initio molecular orbital theory to investigate the effect of the binding energy of the electron on the decay of through-space and through-bond couplings. Through-space and through-bond couplings for anions and cations of the CF3 dimer and of CnH2n and CnF2n chains were calculated by ab initio molecular orbital theory. The anions and cations provide systems for which the electron binding energies, Be, differ by about a factor of 10. Through-space couplings decay exponentially, exp(−βR), with increasing distance, R, between the donor/acceptor carbon atoms. The decay coefficient β varies approximately as B1/2e. In contrast, the decay coefficients for through-bond coupling in CnF2n and CnH2n chains are not affected significantly by the binding energy of the electron. © 1996 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 9201-9205 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We develop a method for measuring absolute two-photon absorption cross sections (σ2) and employ it to determine the σ2 of Rhodamine-6G in methanol (16.2±2.4 GM at 806 nm). Our measurement calibrates the relative excitation spectrum previously reported for this chromophore. The method is based on our derivation of an analytical expression describing the transmission of Gaussian laser pulses through a two-photon absorbing medium. The expression is valid for arbitrary absorber thickness, at all distances from the focus. This generalizes the prevalent "z-scan" (translation of the sample along the beam direction) technique for measuring two-photon absorbance, removing the requirements of a "thin" (thickness (very-much-less-than) Rayleigh range of the focused laser beam) sample and of placing the sample at the focus. This leads to an improvement of the sensitivity of the technique by over two orders of magnitude, enabling measurement of the two-photon absorption cross sections of even weakly absorbing specimens at moderate intensities. The results are significant for applications such as nonlinear microscopy, optical data storage and optical power limiting. © 2000 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 9703-9707 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Portions of the [CH2NO2] potential energy surface related to the OH+HNCO reaction were calculated by means of ab initio molecular orbital theory at the QCISD(T)/6-311++G(d,p) level based on UMP2/6-31G(d,p) optimized geometries. Of all possible three channels considered, the hydrogen abstraction turns out to be the dominant reaction channel. The addition to C atom requires activation energy slightly larger than that of the abstraction but smaller than that of the N addition, in contrast to the H+HNCO reaction. The structural and energetic parameters for the channels thus characterized were further utilized for the calculation of rate constants in the framework of a quantum statistical theory (QRRK). The contributions of the individual reaction channel towards the total rate constant have been examined. Although the OH+HNCO→NH2+CO2 reaction is more exothermic than the hydrogen abstraction OH+HNCO→H2+NCO, it is confirmed that rate constant for CO2 loss is much lower than that of H2O-elimination. The standard heat of formation of the adduct HNC(OH)O is estimated to be ΔHf298=−41.1±3 kcal/mol. © 1997 American Institute of Physics.
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  • 9
    Publication Date: 2015-08-05
    Description: Biochemistry DOI: 10.1021/acs.biochem.5b00593
    Print ISSN: 0006-2960
    Electronic ISSN: 1520-4995
    Topics: Biology , Chemistry and Pharmacology
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  • 10
    Publication Date: 2015-10-28
    Description: The Journal of Physical Chemistry B DOI: 10.1021/acs.jpcb.5b07320
    Electronic ISSN: 1520-5207
    Topics: Chemistry and Pharmacology , Physics
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