Richard J. Saykally

Bio: Richard J. Saykally is an academic researcher from University of California, Berkeley. The author has contributed to research in topics: Spectroscopy & Absorption spectroscopy. The author has an hindex of 94, co-authored 457 publications receiving 40997 citations. Previous affiliations of Richard J. Saykally include University of California & Lawrence Berkeley National Laboratory.

Infrared cavity ringdown spectroscopy of water clusters: O–D stretching bands

Abstract: The infrared O–D stretching spectrum of fully deuterated jet-cooled water clusters is reported. Sequential red-shifts in the single donor O–D stretches, which characterize the cooperative effects in the hydrogen bond network, were accurately measured for clusters up to (D2O)8. Detailed comparisons with corresponding data obtained for (H2O)n clusters are presented. Additionally, rotational analyses of two D2O dimer bands are presented. These measurements were made possible by the advent of infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) using Raman-shifted pulsed dye lasers, which creates many new opportunities for gas phase IR spectroscopy.

Tunable far‐infrared laser spectroscopy of hydrogen bonds: The Ka =0(u)→1(g) rotation–tunneling spectrum of the HCl dimer

Abstract: The ground state K_a =0(u)→1(g) b‐type subband of the rotation–tunneling spectrum of the symmetric ^(35)Cl–^(35)Cl,^(37)Cl–^(37)Cl, and the mixed ^(35)Cl–^(37)Cl hydrogen chloride dimers have been recorded near 26.3 cm^(−1) with sub‐Doppler resolution in a continuous two‐dimensional supersonic jet with a tunable far‐infrared laser spectrometer. Quadrupole hyperfine structure from the chlorine nuclei has been resolved. From the fitted rotational constants a (H^(35)Cl)_2 center‐of‐mass separation of 3.81 A is derived for the K_a =1(g) levels, while the nuclear quadrupole coupling constants yield a vibrationally averaged angular structure for both tunneling states of approximately 20–25 deg for the hydrogen bonded proton and at least 70–75 deg for the external proton. This nearly orthogonal structure agrees well with that predicted by ab initio theoretical calculations, but the observed splittings and intensity alterations of the lines indicate that the chlorine nuclei are made equivalent by a large amplitude tunneling motion of the HCl monomers. A similar geared internal rotation tunneling motion has been found for the HF dimer, but here the effect is much greater. The ground state tunneling splittings are estimated to lie between 15–18 cm^(−1), and the selection rules observed indicate that the trans tunneling path dominates the large amplitude motion, as expected, provided the dimer remains planar. From the observed hyperfine constants, we judge the dimer and its associated tunneling motion to be planar to within 10°.

The far‐infrared vibration–rotation–tunneling spectrum of the water tetramer‐d8

Abstract: The far‐infrared vibration–rotation–tunneling spectrum of (D2O)4 has been measured in the spectral region near 2.04 THz. Observation of additional transition doublets with a constant 5.6 MHz spacing in a parallel (c‐type) spectrum extends the first detailed study of this cluster [Science 271, 59 (1996)]. Three possibilities are explored for the origin of this small splitting: tunneling between degenerate equilibrium structures via facile torsional motions analogous to those observed in the water trimer, tunneling between nondegenerate structural frameworks, and tunneling made feasible only through excitation of a specific vibrational coordinate. The degenerate tunneling scheme best accounts for the spectral features, although the precise dynamics responsible for the observed spectral features cannot be uniquely established from the present data. A further doubling of spectral features, observed only in the K=2 manifold of transitions for J≥3, is symmetric about the unperturbed symmetric top energy levels ...

Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

Abstract: While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.

Fast parallel algorithms for short-range molecular dynamics

Abstract: Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

Abstract: 抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment

Abstract: The optical properties of metal nanoparticles have long been of interest in physical chemistry, starting with Faraday's investigations of colloidal gold in the middle 1800s. More recently, new lithographic techniques as well as improvements to classical wet chemistry methods have made it possible to synthesize noble metal nanoparticles with a wide range of sizes, shapes, and dielectric environments. In this feature article, we describe recent progress in the theory of nanoparticle optical properties, particularly methods for solving Maxwell's equations for light scattering from particles of arbitrary shape in a complex environment. Included is a description of the qualitative features of dipole and quadrupole plasmon resonances for spherical particles; a discussion of analytical and numerical methods for calculating extinction and scattering cross-sections, local fields, and other optical properties for nonspherical particles; and a survey of applications to problems of recent interest involving triangula...

Dye-Sensitized Solar Cells

Abstract: Dye-sensitized solar cells (DSCs) offer the possibilities to design solar cells with a large flexibility in shape, color, and transparency. DSC research groups have been established around the worl ...

Quantum Dot Bioconjugates for Ultrasensitive Nonisotopic Detection

Abstract: Highly luminescent semiconductor quantum dots (zinc sulfide-capped cadmium selenide) have been covalently coupled to biomolecules for use in ultrasensitive biological detection. In comparison with organic dyes such as rhodamine, this class of luminescent labels is 20 times as bright, 100 times as stable against photobleaching, and one-third as wide in spectral linewidth. These nanometer-sized conjugates are water-soluble and biocompatible. Quantum dots that were labeled with the protein transferrin underwent receptor-mediated endocytosis in cultured HeLa cells, and those dots that were labeled with immunomolecules recognized specific antibodies or antigens.