Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

Congruence criteria for finite subsets of complex projective and complex hyperbolic spaces

We investigate congruence classes and direct congruence classes of m-tuples in the complex projective space ℂP ⁿ . For direct congruence one allows only isometries which are induced by linear (instead of semilinear) mappings. We establish a canonical bijection between the set of direct congruence classes of m-tuples of points in ℂP ⁿ and the set of equivalence classes of positive semidefinite Hermitean m×m-matrices of rank at most n+1 with 1's on the diagonal. As a corollary we get that the direct congruence class of an m-tuple is uniquely determined by the direct congruence classes of all of its triangles, provided that no pair of points of the m-tuple has distance π/2. Examples show that the situation changes drastically if one replaces direct congruence classes by congruence classes or if distances π/2 are allowed. Finally we do the same kind of investigation also for the complex hyperbolic space ℂH ⁿ . Most of the results are completely analogous, however, there are also some interesting differences. Received: 15 January 1996     

A dual graph-norm refinement indicator for finite volume approximations of the Euler equations

Summary. We generalise and apply a refinement indicator of the type originally designed by Mackenzie, Süli and Warnecke in [15] and [16] for linear Friedrichs systems to the Euler equations of inviscid, compressible fluid flow. The Euler equations are symmetrized by means of entropy variables and locally linearized about a constant state to obtain a symmetric hyperbolic system to which an a posteriori error analysis of the type introduced in [15] can be applied. We discuss the details of the implementation of the refinement indicator into the DLR--Code which is based on a finite volume method of box type on an unstructured grid and present numerical results. Received May 15, 1995 / Revised version received April 17, 1996     

Kinetics of phenol hydrogenation over supported palladium catalyst

Kinetics of vapor phase hydrogenation of phenol to cyclohexanone over Pd/MgO system has been studied in a flow microreactor under normal atmospheric pressure. The reaction rate is found to be negative order with respect to the partial pressure of phenol and has increased from −0.5 to 0.5 with increasing temperature (473 to 563 K). The apparent activation energy (E_a) of the process is found to be close to 65 kJ per mol. On the basis of kinetic results a surface mechanism is proposed.     

有势场逆问题的边界元法

本文给出了位势方程逆问题的一种最小二乘边界元解法。控制方程为Ｌａｐｌａｃｅ方程，但一部分边界上未给出任何边值，而只在某些内点上给出了势函值。这一问题在数学上属不适定问题，但在一定条件下存在唯一解。本文同时给出了一种估计解的可靠性的方法。数值试验表明，这类逆问题采用边界元法是非常有效的。     

四角晶相HfO2(001)表面原子和电子结构研究

采用基于第一性原理的密度泛函理论研究了四角晶相二氧化铪(t-HfO₂)体相及 其(001)表面的原子几何与电子结构.理论计算结果表明，t-HfO₂(001)表面不会 产生重构现象.与体相电子结构相比, t-HfO₂(001)表面态密度明显高于体相态 密度.其次，表面原子的态密度更靠近费米能级(E_F)，价带往低能量处移动，并 有表面态产生.计算结果表明了t-HfO₂表面禁带宽度明显低于体相的禁带宽度. t-HfO₂(001)的表面态产生以及表面禁带宽度减小是由于Hf原子与O原子的配位 数减少，表面原子周围的环境发生变化而引起的. 关键词： 密度泛函理论 2(001)')" href="#">t-HfO₂(001) 表面电子结构