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101.
A computational study is made of the number of important anharmonic mode-mode couplings in the context of vibrational calculations for di-, tri-, and tetrapeptides. The method employed is the correlation-corrected vibrational self-consistent field (CC-VSCF) algorithm, which includes correlation effects between different vibrational modes. It is found that results of good accuracy can be obtained in calculations that include only N log N mode-mode coupling terms, where N is the number of modes. This simplification significantly accelerates CC-VSCF calculations for large molecules. A criterion based on the characteristics of the normal-mode displacements is employed to predict a priori unimportant coupling terms. The criterion is tested statistically using Spearman's rank correlation coefficient. The results are illustrated by calculations for several di-, tri-, and tetrapeptides using semiempirical PM3 potential surfaces. These results are analyzed and a statistical model for error estimation is given. The decrease in the number of included coupling from N(2) to N log N opens possibilities of anharmonic vibrational calculations for large peptides. 相似文献
102.
Adesokan AA Chaban GM Dopfer O Gerber RB 《The journal of physical chemistry. A》2007,111(31):7374-7381
The results of anharmonic frequency calculations on neutral imidazole (C3N2H4, Im), protonated imidazole (ImH+), and its complexes with water (ImH+)(H2O)n, are presented and compared to gas phase infrared photodissociation spectroscopy (IRPD) data. Anharmonic frequencies are obtained via ab initio vibrational self-consistent field (VSCF) calculations taking into account pairwise interactions between the normal modes. The key results are: (1) Prediction of anharmonic vibrational frequencies on an MP2 ab initio potential energy surface show excellent agreement with experiment and outstanding improvement over the harmonic frequencies. For example, the ab initio calculated anharmonic frequency for (ImH+)(H2O)N2 exhibits an overall average percentage error of 0.6% from experiment. (2) Anharmonic vibrational frequencies calculated on a semiempirical potential energy surface fitted to ab initio harmonic data represents spectroscopy well, particularly for water complexes. As an example, anharmonic frequencies for (ImH+)H2O and (ImH+)(H2O)2 show an overall average deviation of 1.02% and 1.05% from experiment, respectively. This agreement between theory and experiment also supports the validity and use of the pairwise approximation used in the calculations. (3) Anharmonic coupling due to hydration effects is found to significantly reduce the vibrational frequencies for the NH stretch modes. The frequency of the NH stretch is observed to increase with the removal of a water molecule or replacement of water with N2. This result also indicates the ability of the VSCF method to predict accurate frequencies in a matrix environment. The calculation provides insights into the nature of anharmonic effects in the potential surface. Analysis of percentage anharmoncity in neutral Im and ImH+ shows a higher percentage anharmonicity in the NH and CH stretch modes of neutral Im. Also, we observe that anharmonicity in the NH stretch modes of ImH+ have some contribution from coupling effects, while that of neutral Im has no contribution whatsoever from mode-mode coupling. It is concluded that the incorporation of anharmonic effects in the calculation brings theory and experiment into much closer agreement for these systems. 相似文献
103.
M. Merschdorf W. Pfeiffer A. Thon S. Voll G. Gerber 《Applied Physics A: Materials Science & Processing》2000,71(5):547-552
Two-photon photoemission spectroscopy using femtosecond laser pulses is used to investigate the excitation and decay mechanisms
of the surface plasmon resonance in Ag nanoparticles grown on graphite. The resonant excitation of this collective excitation
leads to a two-orders-of-magnitude-enhanced two-photon photoemission yield from a graphite surface with Ag nanoparticles compared
to the yield from pure graphite. From the shape of the photoemission spectra, the polarization dependence of the photoemission
yield and the excitation probabilities for different excitation pathways we conclude that excitation with 400-nm femtosecond
laser pulses leads to the coherent multiple excitation of the surface plasmon in the Ag nanoparticles. This multiply excited
plasmon mode can decay via the coupling to a single-particle excitation leading to the emission of an electron if its final
state is located in the continuum. The surface plasmon in metallic nanoparticles is a model system to investigate collective
excitations in multiphoton processes.
Received: 26 June 2000 / Accepted: 2 September 2000 / Published online: 12 October 2000 相似文献
104.
L. Huang M. Gerber H. Taylor J. Lu E. Tapaszi M. Wutkowski M. Hill C. Lewis A. Harvey A. Herndon M. Wei C.C. Rusa A.E. Tonelli 《Macromolecular Symposia》2001,176(1):129-144
The processing of polymer materials from their inclusion compounds (ICs) formed with urea (U) and cyclodextrin (CD) hosts is described. Several examples are presented and serve to demonstrate the fabrication of unique polymer‐polymer composites and blends, including intimate blends of normally incompatible polymers, and the delivery of additives to polymers by means of embedding polymer‐ or additive‐U and CD‐ ICs into carrier polymer films and fibers, followed by coalescence of the IC guest, or by coalescence of two polymers or a polymer and an additive from their common CD‐IC crystals. 相似文献
105.
Yu Wang Pascal Puech Iann Gerber Alain Pnicaud 《Journal of Raman spectroscopy : JRS》2014,45(3):219-223
Graphite intercalation compounds, due to charge transfer between layers of graphite and intercalants, have a strongly shifted Fermi level. Potassium is known to give its electron leading to a large charge transfer fc close to for stage 1 (KC8) and for stage 2 (KC24). The question is more subtle in stage 3 (KC36) for which the graphene layers are not equivalent. For stage 3, two Raman G bands are clearly visible, corresponding to the interior layer and the boundary layers, respectively. By varying the excitation energy from UV to infrared, we observe that the intensity of the boundary layers G band versus that of the interior layer is maximum at 2.5 eV, leading to a sharp resonance profile at room temperature. Using first‐principle calculation, we associate this transition to π → π∗ of the bounding layers. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
106.
Roman Gerber Miriam Oberholzer Dr. Christian M. Frech 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):2978-2986
Dichloro[bis{1‐(dicyclohexylphosphanyl)piperidine}]palladium [(P{(NC5H10)(C6H11)2})2PdCl2] ( 1 ) is a highly active and generally applicable C? C cross‐coupling catalyst. Apart from its high catalytic activity in Suzuki, Heck, and Negishi reactions, compound 1 also efficiently converted various electronically activated, nonactivated, and deactivated aryl bromides, which may contain fluoride atoms, trifluoromethane groups, nitriles, acetals, ketones, aldehydes, ethers, esters, amides, as well as heterocyclic aryl bromides, such as pyridines and their derivatives, or thiophenes into their respective aromatic nitriles with K4[Fe(CN)6] as a cyanating agent within 24 h in NMP at 140 °C in the presence of only 0.05 mol % catalyst. Catalyst‐deactivation processes showed that excess cyanide efficiently affected the molecular mechanisms as well as inhibited the catalysis when nanoparticles were involved, owing to the formation of inactive cyanide complexes, such as [Pd(CN)4]2?, [(CN)3Pd(H)]2?, and [(CN)3Pd(Ar)]2?. Thus, the choice of cyanating agent is crucial for the success of the reaction because there is a sharp balance between the rate of cyanide production, efficient product formation, and catalyst poisoning. For example, whereas no product formation was obtained when cyanation reactions were examined with Zn(CN)2 as the cyanating agent, aromatic nitriles were smoothly formed when hexacyanoferrate(II) was used instead. The reason for this striking difference in reactivity was due to the higher stability of hexacyanoferrate(II), which led to a lower rate of cyanide production, and hence, prevented catalyst‐deactivation processes. This pathway was confirmed by the colorimetric detection of cyanides: whereas the conversion of β‐solvato‐α‐cyanocobyrinic acid heptamethyl ester into dicyanocobyrinic acid heptamethyl ester indicated that the cyanide production of Zn(CN)2 proceeded at 25 °C in NMP, reaction temperatures of >100 °C were required for cyanide production with K4[Fe(CN)6]. Mechanistic investigations demonstrate that palladium nanoparticles were the catalytically active form of compound 1 . 相似文献
107.
Zhang J Lang HP Yoshikawa G Gerber C 《Langmuir : the ACS journal of surfaces and colloids》2012,28(15):6494-6501
The accessibility and binding affinity of DNA are two key parameters affecting the hybridization efficiency in surface-based biosensor technologies. Better accessibility will result in a higher hybridization efficiency. Often, mixed ssDNA and mercaptohexanol monolayers are used to increase the hybridization efficiency and accessibility of surface-bound oligonucleotides to complementary target DNA. Here, no mercaptohexanol monolayer was used. We demonstrate by differential microcantilever deflection measurements at different pH that the hybridization efficiency peaks between pH 7.5 and 8.5. At low pH 4.5, hydration and electrostatic forces led to tensile surface stress, implying the reduced accessibility of the bound ssDNA probe for hybridization. In contrast, at high pH 8.5, the steric interaction between neighboring ssDNA strands was decreased by higher electrostatic repulsive forces, bending the microcantilever away from the gold surface to provide more space for the target DNA. Cantilever deflection scales with pH-dependent surface hybridization efficiency because of high target DNA accessibility. Hence, by changing the pH, the hybridization efficiency is adjusted. 相似文献
108.
Gerber LC Moser N Luechinger NA Stark WJ Grass RN 《Chemical communications (Cambridge, England)》2012,48(32):3869-3871
Lanthanum oxide nanoparticles were utilized to scavenge phosphate from microbial growth media for the use of targeted nutrient starvation as an antimicrobial strategy. Only in phosphate poor environments a toxic effect was observed. The effect was shown on Escherichia coli, Staphylococcus carnosus, Penicillium roqueforti, and Chlorella vulgaris. 相似文献
109.
Subsurface flaws, which determine the fracture strength of crystals, can be removed by the aid of chemical etching. Above a temperature of 200°C orthophosphoric acid H3PO4 is an efficient etchant for yttrium aluminium garnets. However, at these temperatures the etchant decomposes into its related phosphoric acids which show negligible etching rates for garnets. It takes a long time to warm up a large volume of acid and the etchant is decomposed for the most part already before the optimum temperature is reached. We show that efficient etching is achieved when the samples are in the bath already during the warm-up phase and specify the parameters for the optimum etch process. 相似文献
110.