A Novel Exact Fixed-node Quantum Monte Carlo Algorithm

In this paper we proposed a novel exact fixed-node quantum Monte Carlo (EFNQMC)algorithm,which is a self-optimizing and self-improving procedure,In contrast to the previous EFNQMC method,the trial function is optimized synchronistically in the diffusion procedure,but not before the beginning of EFNQMC computation.In order to optimize the trial function,the improved steepest descent technique is used,in which the step size is automatically adjustable.The procedure is quasi-Newton and converges super linearly.We also use a novel trial function,which has correct electron-electron and electron-nucleus cusp conditions.The novel EFNQMC algorithm and the novel trial function are employed to calculate the energies of 1^1A1 state of CH2,^1Ag state of C8 and the ground-states of H2,LiH,Li2,H2O,respectively.The test results show that both the novel algorithm and the trial function proposed in the present paper are very excellent.     

Ant Colony Algorithm and Optimization of Test Conditions in Analytical Chemistry

The research for the new algorithm is in the forward position and an issue of general interest in chemometrics all along.A novel chemometrics method,Chemical Ant Colony Algorithm,has first been developed.In this paper,the basic principle,theevaluation function,and the parameter choice were discussed.This method has been successfully applied to the fitting of nonlinear multivariate function and the optimization of test conditions in chrome-azure-S-Al spctrophotometric system.The sum of residual square of the results is 0.0009,which has reached a good convergence result.     

A new algorithm for the fixed-node quantum Monte Carlo method

A novel algorithm is proposed for the fixed-node quantum Monte Carlo (FNQMC) method.In contrast to previous procedures,its "guiding function" is not optimized prior to diffusion quantum Monte Carlo (DMC) computation but synchronistically in the diffusion process The new algorithm can not only save CPU time,but also make both of the optimization and diffusion carried out according to the same sampling fashion,reaching the goal to improve each other This new optimizing procedure converges super-linearly,and thus can accelerate the particle diffusion During the diffusion process,the node of the "guiding function" changes incessantly,which is conducible to reducing the "fixed-node error" The new algorithm has been used to calculate the total energies of states X3B1 and a1A1 of CH2 as well as π-X2B1 and λ-2A1 of NH2 The singlet-triplet energy splitting (λEsT) in CH2 and π energy splitting in NH2 obtained with this present method are (45 542±1.840) and (141.644±1.589) kJ/mol,respectively The calculated     

A procedure of determining potential energy surfaces of triatomic molecules from inversion of spectroscopic data

In this paper,we have suggested an iterative procedure of optimization of the linearparameters in an analytic potential energy function for a triatomic molecule,by combining both variational and second order perturbation methods.The most important feature of this procedure is that the objective function is an analytical expression which can be optimized easily.The application to the water molecule is presented.     

An SCF-CI method for determining the potential energy surface of a triatomic molecule

A self-consistent-field (SCF)-configuration interaction (CI) (SCF-CI) method for determining the potential energy surface of a triatomic molecule from the observed vibrational band origins has been suggested. By this method, the SCF-CI procedure in the internal coordinates is used to calculate the vibrational bond origins and their first derivatives with respect to parameters in the potential energy function using the exact vibrational Hamiltonian, and the optimizer LMF in the nonlinear-squares problem is employed to optimize parameters in the potential energy function. This approach is used to optimize the potential energy function of the water molecule. The standard deviation of this fitting to the 70 observed band origins is 1.154cm-1.     

Density matrix method and ultrafast processes

When femto-second (fs) time-resolved experiments are used to study ultrafast processes, quantum beat phenomena are often observed. In this paper, to analyze the fs time-resolved spectra, we will present the density matrix method, a powerful theoretical technique, which describes the dynamics of population and coherence of the system. How to employ it to study the pump-probe experiments and fs ultrafast processes is described. The ππ*→nπ* transition of pyrazine is used as an example to demonstrate the application of the density matrix method. Recently, Suzuki’s group have employed the 22 fs time resolution laser to study the dynamics of the ππ* state of pyrazine. In this case, conical intersection is commonly believed to play an important role in this non-adiabatic process. How to treat the effect of conical intersection on non-adiabatic processes and fs time-resolved spectra is presented. Another important ultrafast process, vibrational relaxation, which takes place in sub-ps and ps range and has never been carefully studied, is treated in this paper. The vibrational relaxation in water dimer is chosen to demonstrate the calculation. It should be noted that the vibrational relaxation of (H2O)2 has not been experimentally studied but it can be accomplished by the pump-probe experiments.     

POTENTIAL VORTICITY ADAPTATION PROCESS IN BAROCLINIC ATMOSPHERE

Starting from the primary equations and using the method of multiple timescale, theauthor derives three stages of baroclinic atm ospheric motion, i.e. the stage of geostrophicadaptation the stage of quasi-geostrophic potential vorticity adaptation and the balanced state.The potential vorticity adaptation comes into being through the process in which long wavesdisperse unbalanced energy. It is demonstrated by means of energy variation that under non-linear condition, the quasi-geostrophic evolution in which the potential vorticity conserves in-evitably leads to a quasi-balanced state. In this balanced state isolines of energy, stream lines andisohypses run parallel with each other. The first order approximation of this balanced stateis the so-called balance equation. Thus in nonlinear atmosphere this balanced state is moregeneral than the quasi-geostrophic balance. This result is significant for mid-range and long-range weather evolution.     

Paired-permanent approach to valence bond theory

A new function called paired-permanent is defined and widely discussed, and a practicable procedure for evaluations of paired-permanents is proposed, which is similar to the Laplace method for determinants. Using the concept of paired-permanents, an efficient algorithm is presented for evaluating the Hamiltonian and overlap matrix elements in the spin-free form of valence bond (VB) theory. With the new algorithm, a spin-free wavefunction is simply written as a paired-permanent, and an overlap matrix element may be obtained by evaluating a corresponding paired-permanent. Meanwhile, the Hamiltonian matrix element is expressed in terms of the summation of the products of electronic integrals and the corresponding sub-paired-permanents     

XPS Characterization of Carbon Nanotube Supported CoMo Hydrodesulfurization Catalysts

In this paper, the effect of catalytic support and sulfiding method on the chemical state of supported Co-Mo catalysts is studied by XPS. After sulfidation with in-situ method, the majority of molybdenum in CNT supported CoMo catalyst is transferred to a species with a formal chemical state Mo(Ⅳ) in MoS2 phase, and the rest to Mo(Ⅴ) which consists of Mo coordinated both to O and S, such as MoO2S2^2- and MoO3S^2-. In case of CoMo/γ-Al2O3 catalyst sulfided with in-situ method, a fraction of molybdenum is transferred to formal state Mo(Ⅳ) in the form of MoS2, but there is still a mount of unreduced Mo(VI) phase which is difficult to be sulfided. In CoMo/CNT catalyric system sulfided with ex-situ method, Mo(IV) in the form of MoS2 is detected along with a portion of unreduced Mo(VI) phase, suggesting that not all the Mo phases are reduced and sulfided by ex-situ method. As for CoMo/γ-Al2O3, a portion of molybdenum is sulfided to intermediate reduced state Mo(V) which consists of Mo coordinated both to O and S, such as MoO2S2^2- and MoO3S^2-, in addition, there is still a fraction of unreduced Mo(Ⅵ)phase. XPS analyses results suggest that CNT support facilitates the reduction and sulfidation of active species to a large extent, and that alumina support strongly interacts with active species, hereby producing a fraction of phase which resists complete sulfiding. Catalytic measurements of catalysts in the HDS of dibenzothiophene (DBT) show that CoMo/CNT catalysts are of higher HDS activity and selectivity than CoMo/γ-Al2O3 catalyst, which is in good relation with the sulfiding behavior of the corresponding catalyst.     

Preparation of true solutions of monomeric amyloidogenic protein/peptide: A critical prerequisite for aggregation kinetic study

Our dynamic laser light scattering(LLS) study shows that the current widely used protocols of dissolving amyloidogenic protein/peptide do not really result in a true solution;namely,there always exist a trace amount of interchain aggregates,which greatly affect the association kinetics,partially explaining why different kinetics were reported even for a solution with identical protein and solvent.Recently,using a combination of the conventional dissolution procedure and our newly developed ultra-filtration method,we have developed a novel protocol to prepare a true solution of amyloidogenic protein/peptide without any interchain aggregates.The resultant solutions remain in their monomeric state for at least one week,which is vitally important for further study of the very initial stage of the interchain association under the physiological conditions because more and more evidence suggests that it is those small oligomers rather than large fabric aggregates that are cytotoxic.In addition,this study shows that combining static and dynamic LLS can lead to more physical and microscopic information about the protein association instead of only the size distribution.     

自优化剩余函数量子Monte Carlo方法

提出剩余函数量子Monte Carlo的一个新算法，这是一个自优化和自改善的过程.与以前的算法相比，本算法中的试探函数的优化是在剩余函数方法中同步进行的，而不是在变分Monte Carlo计算之前.为了优化试探函数，使用一种改进了的速降法，这是一个步长能够自动调节，超线性收敛的优化技术.在这个算法中,还使用了一种新的相关函数，它满足电子与电子以及电子与核奇点条件.此方法已被用于计算H2、LiH、Li2、H2O分子的基态以及CH2的X 3B1态、1 1A1态和2 1A1态的能量值.     

用变分Monte Carlo方法处理分子

对变分量子Ｍｏｎｔｅ Ｃａｒｔｏ方法提出了一种种算法：将传统的Ｈａｒｔｒｅｅ－Ｆｏｅｋ方法与量子Ｍｏｎｔｅ Ｃａｒｌｏ方法有机结合在一起；导出了“局部能”的解析式；使用了一种新的相关函数和随机数发生器。我们用这个新算法计算了Ｈ２、ＬｉＨ、Ｌｉ２、Ｈ２Ｏ、Ｆ２分子的基态和ＣＨ２分子的＾３Ｂ１、＾１Ａ１态的能量。计算结果表明，这个新算法在精度和统计误差两个方面比一般ＶＭＣ过程都要好得多。     

Fixed—node Quantum Monte Carlo：A Novel Approach

The fixed-node quantum Monte Carlo (FNQMC)1,2 method has made it possible to calculate the electronic structure of relatively large molecular systems. These large systems range from positron complexes [NH2, Ps] with ～10 electrons to C20 isomers with 120 electrons, silicon crystal structures of 250 atoms and 1000 valence electrons. In the practical calculation for FNQMC method, in general, a minimal basis set of Slater-type atomic orbital (STO) and Jastrow functions are taken to cons…     

Adaptive importance sampling Monte Carlo simulation of rare transition events

We develop a general theoretical framework for the recently proposed importance sampling method for enhancing the efficiency of rare-event simulations [W. Cai, M. H. Kalos, M. de Koning, and V. V. Bulatov, Phys. Rev. E 66, 046703 (2002)], and discuss practical aspects of its application. We define the success/fail ensemble of all possible successful and failed transition paths of any duration and demonstrate that in this formulation the rare-event problem can be interpreted as a "hit-or-miss" Monte Carlo quadrature calculation of a path integral. The fact that the integrand contributes significantly only for a very tiny fraction of all possible paths then naturally leads to a "standard" importance sampling approach to Monte Carlo (MC) quadrature and the existence of an optimal importance function. In addition to showing that the approach is general and expected to be applicable beyond the realm of Markovian path simulations, for which the method was originally proposed, the formulation reveals a conceptual analogy with the variational MC (VMC) method. The search for the optimal importance function in the former is analogous to finding the ground-state wave function in the latter. In two model problems we discuss practical aspects of finding a suitable approximation for the optimal importance function. For this purpose we follow the strategy that is typically adopted in VMC calculations: the selection of a trial functional form for the optimal importance function, followed by the optimization of its adjustable parameters. The latter is accomplished by means of an adaptive optimization procedure based on a combination of steepest-descent and genetic algorithms.     

Automatic assignment of 1H‐NMR spectra of small molecules

A novel data‐evaluation procedure for the automatic atom to peak or multiplet assignment of ¹H‐NMR spectra of small molecules has been developed using a fast and robust expert system. The applicability and reliability of the method are demonstrated by comparison of a manually assigned database of ¹H‐NMR spectra with the assignments produced by the automatic procedure. The results of this analysis show an excellent success ratio, indicating that this new algorithm can have a major impact as a time saving tool for the organic chemist. A new graphical feature used to illustrate both the stability and quality of the elementary assignments is also introduced. Copyright © 2013 John Wiley & Sons, Ltd.     

量子Monte Carlo固定节面法试探函数研究

量子ＭｏｎｔｅＣａｒｌｏ固定节面法试探函数研究黄宏新曹泽星（湖南师范大学化学系长沙４１００８１）关键词量子ＭｏｎｔｅＣａｒｌｏ方法试探函数奇点条件固定节面量子ＭｏｎｔｅＣａｒｌｏ（ＦＮＱＭＣ）方法是ＱＭＣ方法中使用最多的一种，它的试探函数一般是这样组...     

An application of the refined born approximation to the solution of coupled equations involved in electron-ion and electron-atom scattering problems

A new approach to the solution of coupled equations involved in electron-ion and electron-atom scattering problems is proposed. This method is a combination of iteration and variation procedures. The main advantage of this method is that exchange terms can be calculated in a direct and straightforward manner. The method is based on the Lippmann-Schwinger equation and does not require trial functions satisfying appropriate boundary conditions. Using the Volterra formulation one can find the solution on an interval determined by the range of the exchange potential and the long-range potential terms can be taken into account by a projection procedure giving the asymptotic value of the reactance matrix. The method is tested on the case of electron-hydrogen atom scattering in the 1s-2s and 1s-2s-2p approximation.We have adapted the method proposed originally by Rayski to obtain solutions of coupled equations involved in electron-ion and electron-atom scattering. As mentioned in section 1 the construction of the method secures an automatic fulfilment of the boundary conditions. It allows an easy calculation of the exchange potential as well as an estimation of the introduced approximation. It gives also a possibility of detecting any spurious convergence. Moreover, it is important that this formalism can be applied in the case of normalized as well as unnormalized initial integral equations. This fact is of special importance in the case of long-range interactions. When the method is used for unnormalized (Volterra) equations it allows application of a very convenient projection procedure for treating the long-range terms in the direct potential.Electron-hydrogen atom collisions are investigated as a numerical illustration of the method. In the 1s-2s approximation the normalized equations were solved, while in the 1s-2s-2p approximation the solution was obtained with the help of Volterra equations and the long-range terms of the direct potential were taken into account by the projection procedure. In both cases the calculations were performed in the first iteration step and the obtained solutions agree fairly well with the results obtained by a numerical integration. It is not clear which set of results is more accurate. The numbers of parameters needed to obtain these results was not too large (not more than twenty in each channel) and decreased with the increase of the values of angular momentum and energy. The calculations were performed without weight functions, although the use of an appropriate weight function can improve the effectiveness of the method. This effectiveness could also be improved through a more lucky choice of trial functions.     

A density functional theory-time-dependent density functional theory investigation of photo-induced hydrogen bond and proton transfer for 2-(3,5-dichloro-2,6-dihydroxy-phenyl)-benzoxazole-6-carboxylicacid

Given the paramount importance of excited-state relaxation in the photochemical process, excited-state hydrogen bonding interactions and excited-state intramolecular proton transfer (ESIPT) are always hot topics. In this work, we theoretically explore the excited-state dynamical behaviors for a novel 2-(3,5-dichloro-2,6-dihydroxy-phenyl)-benzoxazole-6-carboxylicacid (DDPBC) system. As two intramolecular hydrogen bonds (O1 H2⋯N3 and O4 H5⋯O6) exist in the DDPBC structure, we first check if the double proton transfer form cannot be formed in the S1 state. Then, we explore the changes of geometrical parameters involved in hydrogen bonds, based on which we confirm that the dual intramolecular hydrogen bonds are strengthened on photo-excitation. The O1 H2⋯N3 hydrogen bond particularly plays a more important role in excited state. When it comes to the photo-induced excitation, we find charge transfer and electronic density redistribution around O1 H2 and N3 atom moieties. We verify the ESIPT tendency arising from the O1 H2⋯N3 hydrogen bond. In the analysis of the potential energy curves, along with O1 H2⋯N3 and O4 H5⋯O6, we demonstrate that the ESIPT reaction should occur along with O1 H2⋯N3 rather than O4 H5⋯O6. This work not only clarifies the specific ESIPT mechanism for DDPBC system but also paves the way for further novel applications based on DDPBC structure in the future.