A STUDY ON THE RECONSTRUCTION OF THE EIGHTEENTH CENTURY MEIYU (PLUM RAINS) ACTIVITY OF LOWER CHANGJIANG(YANGTZE) REGION OF CHINA

This study presents a scheme for delimiting the meiyu period in the Lower Changjiang (Yangtze) region. This scheme was applied to the Clear and Rain Records of Nanjing, Suzhou and Hangzhou to reconstruct the 1723-1800 meiyu climate series. The beginning and ending dates, length, precipitation, and the intensity grades of meiyu were determined. The years of early, heavy, light, and empty meiyu were also given. Statistical analyses of the 18th century meiyu series indicate the existence of the quasi-periodicities of 2-3, 4-5, and 9 years. Many basic characteristics of the modern meiyu also existed in the 18th century. Some characteristics of the Northwest Pacific Subtropical High in the 18th century in typical meiyu years were inferred from the historical meiyu series.     

The interaction of carbohydrates and amino acids with aromatic systems studied by density functional and semi-empirical molecular orbital calculations with dispersion corrections

Density functional theory (DFT-D) and semi-empirical (PM3-D) methods having an added dispersion correction have been used to study stabilising carbohydrate-aromatic and amino acid-aromatic interactions. The interaction energy for three simple sugars in different conformations with benzene, all give interaction energies close to 5 kcal mol(-1). Our original parameterization of PM3 (PM3-D) seriously overestimates this value, and has prompted a reparametrization which includes a modified core-core interaction term. With two additional parameters, the carbohydrate complexes, as well as the S22 data set, are well reproduced. The new PM3 scheme (PM3-D*) is found to describe the peptide bond-aromatic ring interactions accurately and, together with the DFT-D method, it is used to investigate the interaction of six amino acids with pyrene. Whilst the peptide backbone can adopt both stacked and T-shaped structures in the complexes with similar interaction energies, there is a preference for the unsaturated ring to adopt a stacked structure. Thus, peptides in which the latter interactions are maximised are likely to be the most effective for the functionalisation of carbon nanotubes.     

Formation of interstellar 2,4-pentadiynylidyne, HCCCCC(X 2Pi), via the neutral-neutral reaction of ground state carbon atom, C(3P), with diacetylene, HCCCCH(X 1Sigma(g)+)

The interstellar reaction of ground-state carbon atom with the simplest polyyne, diacetylene (HCCCCH), is investigated theoretically to explore probable routes to form hydrogen-deficient carbon clusters at ultralow temperature in cold molecular clouds. The isomerization and dissociation channels for each of the three collision complexes are characterized by utilizing the unrestricted B3LYP/6-311G(d,p) level of theory and the CCSD(T)/cc-pVTZ calculations. With facilitation of RRKM and variational RRKM rate constants at collision energies of 0-10 kcalmol, the most probable paths, thus reaction mechanism, are determined. Subsequently, the corresponding rate equations are solved that the evolutions of concentrations of collision complexes, intermediates, and products versus time are obtained. As a result, the final products and yields are identified. This study predicts that three collision complexes, c1, c2, and c3, would produce a single final product, 2,4-pentadiynylidyne, HCCCCC(X (2)Pi), C(5)H (p1)+H, via the most stable intermediate, carbon chain HC(5)H (i4). Our investigation indicates the title reaction is efficient to form astronomically observed 2,4-pentadiynylidyne in cold molecular clouds, where a typical translational temperature is 10 K, via a single bimolecular gas phase reaction.     

Parameterization of daily solar global ultraviolet irradiation

Daily values of solar global ultraviolet (UV) B and UVA irradiation as well as erythemal irradiation have been parameterized to be estimated from pyranometer measurements of daily global and diffuse irradiation as well as from atmospheric column ozone. Data recorded at the Meteorological Observatory Potsdam (52 degrees N, 107 m asl) in Germany over the time period 1997-2000 have been used to derive sets of regression coefficients. The validation of the method against independent data sets of measured UV irradiation shows that the parameterization provides a gain of information for UVB, UVA and erythemal irradiation referring to their averages. A comparison between parameterized daily UV irradiation and independent values of UV irradiation measured at a mountain station in southern Germany (Meteorological Observatory Hohenpeissenberg at 48 degrees N, 977 m asl) indicates that the parameterization also holds even under completely different climatic conditions. On a long-term average (1953-2000), parameterized annual UV irradiation values are 15% and 21% higher for UVA and UVB, respectively, at Hohenpeissenberg than they are at Potsdam. Daily global and diffuse irradiation measured at 28 weather stations of the Deutscher Wetterdienst German Radiation Network and grid values of column ozone from the EPTOMS satellite experiment served as inputs to calculate the estimates of the spatial distribution of daily and annual values of UV irradiation across Germany. Using daily values of global and diffuse irradiation recorded at Potsdam since 1937 as well as atmospheric column ozone measured since 1964 at the same site, estimates of daily and annual UV irradiation have been derived for this site over the period from 1937 through 2000, which include the effects of changes in cloudiness, in aerosols and, at least for the period of ozone measurements from 1964 to 2000, in atmospheric ozone. It is shown that the extremely low ozone values observed mainly after the eruption of Mt. Pinatubo in 1991 have substantially enhanced UVB irradiation in the first half of the 1990s. According to the measurements and calculations, the nonlinear long-term changes observed between 1968 and 2000 amount to +4%, ..., +5% for annual global irradiation and UVA irradiation mainly because of changing cloudiness and + 14%, ..., +15% for UVB and erythemal irradiation because of both changing cloudiness and decreasing column ozone. At the mountain site, Hohenpeissenberg, measured global irradiation and parameterized UVA irradiation decreased during the same time period by -3%, ..., -4%, probably because of the enhanced occurrence and increasing optical thickness of clouds, whereas UVB and erythemal irradiation derived by the parameterization have increased by +3%, ..., +4% because of the combined effect of clouds and decreasing ozone. The parameterizations described here should be applicable to other regions with similar atmospheric and geographic conditions, whereas for regions with significantly different climatic conditions, such as high mountainous areas and arctic or tropical regions, the representativeness of the regression coefficients would have to be approved. It is emphasized here that parameterizations, as the one described in this article, cannot replace measurements of solar UV radiation, but they can use existing measurements of solar global and diffuse radiation as well as data on atmospheric ozone to provide estimates of UV irradiation in regions and over time periods for which UV measurements are not available.     

Improved parameterization of the quantum harmonic oscillator model based on localized wannier functions to describe Van der Waals interactions in density functional theory

Recently, the quantum harmonic oscillator model has been combined with maximally localized Wannier functions to account for long‐range dispersion interactions in density functional theory calculations (Silvestrelli, J. Chem. Phys. 2013, 139, 054106). Here, we present a new, improved set of values for the three parameters involved in this scheme. To test the new parameter set we have computed the potential energy curves for various systems, including an isolated Ar2 dimer, two N2 dimers interacting within different configurations, and a water molecule physisorbed on pristine graphene. While the original set of parameters generally overestimates the interaction energies and underestimates the equilibrium distances, the new parameterization substantially improves the agreement with experimental and theoretical reference values. © 2016 Wiley Periodicals, Inc.     

微合金钢中稀土对沉淀相和性能的影响

在Nb(Ti,V）微合金钢中，主要沉淀相分别为Nb(C,N),(Nb,Ti)(C,N)和V（C，N）。稀土降低沉淀相完全溶解的温度，增大奥氏体中沉淀相析出的孕育期，降低析出速率，抑制奥氏体中沉淀相的析出，在铁素体相区，稀土提高沉淀相的析出速率和数量，促进沉淀相的析出，其中稀土对铌沉淀相析出的作用影响最强。锻态钢中，稀土有促进细化球化析出相的作用，随稀土含量增加，沉淀相析出数量增加，但过量稀土，促进作用又减弱，稀土在保持微合金钢强度的情况下，显著改善其冲击韧性，尤其是低温韧性，微合金钢中添加适量稀土可获得更佳的综合性能。     

THREE-DIMENSIONAL NUMERICAL SIMULATIONS OF THE EFFECTS OF ICE PHASE PROCESSES ON EVOLUTION OF CONVECTIVE STORMS

The numerical experiments on sensitivity of two types of convective storms to ice phasemicrophysical processes have been made by using a fully elastic three-dimensional cloud mod-el with a more detailed ice phase parameterization scheme. The simulations show that, ingeneral, inclusion of ice phase processes in the model leads to more intensive modelingstorms--the total latent heat released and the total precipitation increase obviously, the cloudtop rises, and the maximum ground precipitation rate is reached earlier. These effects of icephase processes can be much more significant in some relatively cold environments, in whichthey even modify the dynamic structures and life cycle of simulating storms. The mecha-nisms and favourable conditions of ice phase influences on storms are also discussed.     

Total reaction probabilities for translationally hot (3.7 eV)D atoms reacting with H2 and their astrophysical implications

Translationally hot (3.7 eV center-of-mass collision energy) D atoms can be produced by the dissociative recombinationsof DCO⁺ ions with electrons in interstellar clouds. The reactions of hot D atoms with H₂ molecules is an important factor in determining the D to H abundance ratio in the universe from observations of deuterated species in dense interstellar clouds. A simulation of this reaction has been carried out using exact quasiclassical reaction cross sections, together with a series of approximate total collision cross sections. It was found that the total probability of reaction, P^R, at 3.7 eV was approximately 0.4. A reaction probability of this magnitude suggeststhat the loss of D atoms by the title reaction be considered in astrochemical modeling of deuterated molecules.     

Van der Waals interactions: evaluations by use of a statistical mechanical method

In this work the induced van der Waals interaction between a pair of neutral atoms or molecules is considered by use of a statistical mechanical method. With use of the Schro?dinger equation this interaction can be obtained by standard quantum mechanical perturbation theory to second order. However, the latter is restricted to electrostatic interactions between dipole moments. So with radiating dipole-dipole interaction where retardation effects are important for large separations of the particles, other methods are needed, and the resulting induced interaction is the Casimir-Polder interaction usually obtained by field theory. It can also be evaluated, however, by a statistical mechanical method that utilizes the path integral representation. We here show explicitly by use of this method the equivalence of the Casimir-Polder interaction and the van der Waals interaction based upon the Schro?dinger equation. The equivalence is to leading order for short separations where retardation effects can be neglected. In recent works [J. S. H?ye, Physica A 389, 1380 (2010); Phys. Rev. E 81, 061114 (2010)], the Casimir-Polder or Casimir energy was added as a correction to calculations of systems like the electron clouds of molecules. The equivalence to van der Waals interactions indicates that the added Casimir energy will improve the accuracy of calculated molecular energies. Thus, we give numerical estimates of this energy including analysis and estimates for the uniform electron gas.     

Crossed beam study of the atom-radical reaction of ground state carbon atoms (C(3P)) with the vinyl radical (C2H3(X2A'))

The atom-radical reaction of ground state carbon atoms (C((3)P)) with the vinyl radical (C(2)H(3)(X(2)A')) was conducted under single collision conditions at a collision energy of 32.3 ± 2.9 kJ mol(-1). The reaction dynamics were found to involve a complex forming reaction mechanism, which is initiated by the barrier-less addition of atomic carbon to the carbon-carbon-double bond of the vinyl radical forming a cyclic C(3)H(3) radical intermediate. The latter has a lifetime of at least 1.5 times its rotational period and decomposes via a tight exit transition state located about 45 kJ mol(-1) above the separated products through atomic hydrogen loss to the cyclopropenylidene isomer (c-C(3)H(2)) as detected toward cold molecular clouds and in star forming regions.     

Complexes of molecular oxygen with organic ligands

Conclusion The values of the paramagnetic shifts and their temperature dependence indicate that the interaction of molecular oxygen with various organic molecules is specific and localized in character; that is it takes place in complexes and not in collision contact pairs. Interactions in collision pairs would not have led to the experimentally observed marked differences in the paramagnetic shifts and their temperature dependence for different fragments of the same molecule, since the orientations of the partners in these pairs are random and almost equally probable.The concentration dependence of the paramagnetic shifts in the water-acetone mixture is described by a scheme involving complex formation with competing ligands. It indicates that oxygen does not form complexes with hydrogen bonds, as might have been expected from an analysis of the values of the paramagnetic shifts for different functional groups of the molecules, but forms complexes of the donor-acceptor type, in which oxygen acts as an electron acceptor.The transfer of spin density from the oxygen molecule to the ligands indicates that collectivization of the electron clouds of oxygen and the ligand takes place in the complex, with the formation of common molecular orbitals. This transfer of spin density by itself can be regarded as an indication or criterion of complex formation (particularly in the case of weak short-lived complexes).Institute of Chemical Physics, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 18, No. 5, pp. 817–823, September–October, 1977.     

Anisotropic interactions from double rainbows in Na atom—molecule collisions

Crossed molecular beam experiments have been performed measuring differential cross sections for Na scattered from CH₃I, (CH₃)₃CCl, (CH₃)₃CBr and (CH₃)₃CI at collision energies of 0.170 to 0.220 eV. The angular distributions show pronounced double rainbow structure which is attributed to the anisotropy of the interaction potential. The origin and the conditions for this structure are investigated by calculations in the infinite order sudden approximation. The effect is used to determine the anisotropic interaction potentials for the measured systems which all exhibit minima in the linear configuration of the collision complex ranging from 30 to 60 meV.     

STUDY ON THE MOISTURE PASSAGE ON THE LOWER REACHES OF THE YARLUNG ZANGBO RIVER

A series of gorges on the lower reaches of the Yarlung Zangbo River is like an enormous crevice splitting the southeastern Qinghai-Xizang (Tibet)Plateau to create a passage through which warm, wet air flow from the Indian Ocean reaches the inner part of the plateau. This moisture passage was mainly strengthened after the Pleistocene epoch in the Quaternary period and has played a major role in affecting the beginning date of the rainy season and the amount of the plateau's rainfall. It has also served as a corridor for the living things on the southern and the northern sides of the Himalayas to mingle with each other. The region along this passage is abundant in evidences of species of differentiation, variation and biological division. Also the passage has provided a favorable environment for human beings and affected natural phenomena there.     

Electron Delocalization in Perylene Diimide Helicenes

We report two new helicenes derived from the double fusion of an acene with two perylene diimide (PDI) subunits. These PDI‐helicene homologs exhibit very different structural and electronic properties, despite differing by only a single ring in the link between the PDI units. The shorter inter‐PDI link brings the two PDI subunits closer together, and this results in the collision of their respective π‐electron clouds. This collision facilitates intramolecular through‐space electronic delocalization when the PDI‐helicene is reduced.     

Reaction of cyanoacetylene HCCCN(X 1Sigma+) with ground-state carbon atoms C(3P) in cold molecular clouds

The reaction of the simplest cyanopolyyne, cyanoacetylene [HCCCN(X (1)Sigma(+))], with ground-state atomic carbon C((3)P) is investigated theoretically to explore the probable routes for the depletion of the famed interstellar molecule HCCCN, and the formation of carbon-nitrogen-bearing species in extraterrestrial environments particularly of ultralow temperature. Six collision complexes (c1-c6) without entrance barrier as a result of the carbon atom addition to the pi systems of HCCCN are located. The optimized geometries and harmonic frequencies of the intermediates, transition states, and products along the isomerization and dissociation pathways of each collision complex are obtained by utilizing the unrestricted B3YLP6-311G(d,p) level of theory, and the corresponding CCSD(T)/cc-pVTZ energies are calculated. Subsequently, with the facilitation of Rice-Ramsperger-Kassel-Marcus (RRKM) and variational RRKM rate constants at collision energy of 0-10 kcal/mol, the most probable paths for the titled reaction are determined, and the product yields are estimated. Five collision complexes (c1-c3, c5, and c6) are predicted to give the same products, a chained CCCCN (p2)+H, via the linear and most stable intermediate, HCCCCN (i2), while collision complex c4 is likely to dissociate back to C+HCCCN. The study suggests that this class of reaction is an important route to the destruction of cyanoacetylene and cyanopolyynes in general, and to the synthesis of linear carbon-chained nitriles at the temperature as low as 10 K to be incorporated in future chemical models of interstellar clouds.     

Improved dissipative particle dynamics simulations of lipid bilayers

The authors introduce a new parameterization for the dissipative particle dynamics simulations of lipid bilayers. In this parameterization, the conservative pairwise forces between beads of the same type in two different hydrophobic chains are chosen to be less repulsive than the water-water interaction, but the intrachain bead interactions are the same as the water-water interaction. For a certain range of parameters, the new bilayer can only be stretched up to 30% before it ruptures. Membrane tension, density profiles, and the in-plane lipid diffusion coefficient of the new bilayer are discussed in detail. They find two kinds of finite size effects that influence the membrane tension: lateral finite size effects, for which larger membranes rupture at a smaller stretch, and transverse finite size effects, for which tensionless bilayers are more compact in larger systems. These finite size effects become rather small when the simulation box is sufficiently large.     

On the possibility of using model potentials for collision integral calculations of interest for planetary atmospheres

The interaction energy in systems (atom–atom, atom–ion and atom–molecule) involving open-shell species, predicted by a phenomenological method, is used for collision integral calculations. The results are compared with those obtained by different authors by using the complete set of quantum mechanical interaction potentials arizing from the electronic configurations of separate partners. A satisfactory agreement is achieved, implying that the effect of deep potential wells, present in some of the chemical potentials, is cancelled by the effect of strong repulsive potentials.     

Investigations of ground-based clouds at the Mt. Brocken

Results of the 1996 field season (April-November) of the cloud chemistry program starting in 1992 at the Mt. Brocken are presented. The mountain site (1142 m a.s.l.) is located in the Harz Mountains/Germany. For a large part of the database (about 40%), both cloud water and drizzle and/or precipitation were present at the same time. A separation into two groups was done: non-precipitating clouds and mixed category of events. More than 2000 one hour samples were collected and analysed for major ions. The mean cloud water pH for the frostfree period in 1996 was 3.9. Histograms giving the distribution of pH values show that the pH values of samples from non-precipitating clouds ranges from 2.5 up to values > 8 and that the distribution is bimodale. For the 1996 field season period as a whole, pH values of cloud water were lower than those of mixed samples (cloud water, drizzle, precipitation) at the Brocken site. This was related to higher concentrations of all ions in cloud water. Cloud base measurements using a ceilometer confirmed the correlation between liquid water content and height above cloud base and consequently the influence of sampling height relative to the cloud base on the total ionic content of cloud water. Received: 17 November 1997 / Revised: 4 February 1998 / Accepted: 9 February 1998     

Density functional theory (DFT)-based modified embedded atom method potentials: Bridging the gap between nanoscale theoretical simulations and DFT calculations

A density functional theory (DFT)-calculation scheme for constructing the modified embedded atom method (MEAM) potentials for face-centered cubic (fcc) metals is presented. The input quantities are carefully selected and a more reliable DFT approach for surface energy determination is introduced in the parameterization scheme, enabling MEAM to precisely predict the surface and nanoscale properties of metallic materials. Molecular dynamics simulations on Pt and Au crystals show that the parameterization empl...