Accurate integration over atomic regions bounded by zero‐flux surfaces

The approach for the integration over a region covered by zero‐flux surface is described. This approach based on the surface triangulation technique is efficiently realized in a newly developed program TWOE . The elaborated method is tested on several atomic properties including the source function. TWOE results are compared with those produced by using well‐known existing programs. Absolute errors in computed atomic properties are shown to range usually from 10^?6 to 10^?5 au. The demonstrative examples prove that present realization has perfect convergence of atomic properties with increasing size of angular grid and allows to obtain highly accurate data even in the most difficult cases. It is believed that the developed program can be bridgehead that allows to implement atomic partitioning of any desired molecular property with high accuracy. © 2012 Wiley Periodicals, Inc.     

不同光场二阶相干度的实验研究

基于Hanbury Brown-Twiss(HBT)实验,我们借助于两个单光子计数模块,一个50/50分束器和一个快速计数卡(FastCom-P7888)研究了不同光场的二阶相干度。我们首先制备了脉冲相干光,连续相干光以及单原子发出的单光子源,并测量这几种不同光场的二阶相干度g(2)(τ)。我们通过测量俘获在磁光阱(MOT)和远失谐偶极阱(FORT)中的单原子在近共振连续激光激发下所辐射的荧光的二阶相干度,分别得到了g(2)(τ=0)=0.08和g(2)(τ=0)=0.09,借助于实验中产生的脉冲光与单原子,接下来我们将进行触发式单光子源的实验研究。     

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

The topology of the molecular electron density of benzene dithiol gold cluster complex Au₄−S−C₆H₄−S′−Au′₄ changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.     

Photochemistry in Real Space: Batho- and Hypsochromism in the Water Dimer

The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born–Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H₂O)₂. It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism. The methods exploited and illustrated herein are able to maintain the individuality and properties of the interacting entities in a molecular aggregate, and thereby they allow chemical intuition in general states, at any geometry and using a broad variety of electronic structure methods to be kept and built.     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

Temps de cohérence d'un condensat de Bose–Einstein dans un gaz isolé harmoniquement piégé

We study the condensate phase dynamics in a low-temperature equilibrium gas of weakly interacting bosons, harmonically trapped and isolated from the environment. We find that at long times, much longer than the collision time between Bogoliubov quasi-particles, the variance of the phase accumulated by the condensate grows with a ballistic term quadratic in time and a diffusive term affine in time. We give the corresponding analytical expressions in the limit of a large system, in the collisionless regime and in the ergodic approximation for the quasi-particle motion. When properly rescaled, they are described by universal functions of the temperature divided by the Thomas–Fermi chemical potential. The same conclusion holds for the mode damping rates. Such universality class differs from the previously studied one of the homogeneous gas.     

Calculations on polarization properties of alkali metal atoms using Dirac–Fock plus core polarization method

A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is then treated in a semiempirical core polarization potential. As an application, the polarization properties of alkali metal atoms, including the static polarizabilities and long-range two-body dispersion coefficients, have been calculated. Our results are in good agreement with the results obtained from ab initio relativistic many-body perturbation method and the available experimental measurements.