Theoretical Study on Hydrogen Bonding of Mono‐ and Dihydrated Complexes of 7‐(3′‐Pyridyl)indole in Excited States

The intermolecular hydrogen bonds of mono‐ and dihydrated complexes of 7‐(3′‐Pyridyl)indole (7‐3′PI) have been investigated using the time‐dependent density functional theory (TD‐DFT) method. The electrostatic potential analysis of monomer 7‐3′PI and 7‐(3′‐Pyridyl)indole‐water (7‐3′PI‐W) indicates that an intermolecular hydrogen bond between two waters can be formed for 7‐(3′‐Pyridyl)indole‐2water (7‐3′PI‐2W) complex. The calculated bond lengths of the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W in the S₁ state (the first excited singlet state) are all shortened compared to the ground state. By the analysis of bond length, charge population and infrared spectra, it is demonstrated that the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W are all strengthened upon electronic excitation to the S1 state. Moreover, the fluorescence of 7‐3′PI‐W and 7‐3′PI‐2W are all red‐shifted to larger wavelength compared to monomer 7‐3′PI. The red‐shift of fluorescence peak of 7‐3′PI‐W and 7‐3′PI‐2W should be attributed to the change of hydrogen bond interaction before and after photoexcitation. Therefore, it can be concluded that the intermolecular hydrogen bonding strengthening in the excited S₁ state induces the fluorescence weakening of 7‐3′PI.     

水中空气隔层衰减冲击波性能研究

 根据鱼雷对舰船毁伤的特点,建立了多介质水下爆炸数值模型,提出了交界面处理及广义光滑长度计算方法,编制了多介质水下爆炸计算程序,并对水下爆炸空气隔层衰减冲击波的性能进行了定量分析。结果表明：无论是接触爆炸还是非接触爆炸,空气隔层均可有效衰减冲击波,并且接触爆炸中空气隔层衰减冲击波的效果更好,最大可使冲击压力峰值降低约55%;空气隔层厚度与爆炸厚度之比为1时便可达到较好的衰减冲击波效果,继续增加空气隔层厚度对衰减冲击波效果影响不大。研究结果可为舰船结构防护及防雷舱的结构设计提供参考。     

Excited-state hydrogen bonding and deprotonation of esculetin in solution: a DFT/TDDFT study

The combined density functional theory (DFT) and time-dependent density functional theory (TDDFT) method was used to study the electronic spectral properties of different deprotonated forms of esculetin. By comparing the experimental absorption and fluorescence bands with the calculated electronic spectra, it is evidently demonstrated that the minor absorption and fluorescence bands observed at slightly longer wavelengths than the principal bands in experiments are predominantly from the de-H3 form of the esculetin monomer. Furthermore, we clarified the relationship between electronic spectral shifts and electronic excited-state intramolecular hydrogen bonding changes: the strengthening of intramolecular hydrogen bond can induce an electronic spectral blueshift while the intramolecular hydrogen bond weakening can result in an electronic spectral redshift.     

The effect of intragranular microstress in Al2O3—SiC nanocomposites

A theoretical model is established to investigate the intragranular particle residual stress in Al2O3-SiC nanocomposites.Using this model,we calculate the average compressive stress on the Al2O3 grain boundary(GB) and the average tensile stress within Al2O3 grains caused by SiC nanoparticles.The normal compressive stress strengthens the GB,and the average tensile stress weakens the grains.The model gives a reasonable interpretation of the strength changes of Al2O3-SiC nanocomposites with the number of SiC particles.     

Excited‐State Hydrogen Bonding Strengthening and Weakening with Intramolecular Charge Transfer in Resorufin‐Water Complexes: A TD‐DFT Study

The geometric structures, infrared spectra and hydrogen bond binding energies of the various hydrogen‐bonded Res^?‐water complexes in states S0 and S1 have been calculated using the density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) methods, respectively. Based on the changes of the hydrogen bond lengths and binding energies as well as the spectral shifts of the vibrational mode of the hydroxyl groups, it is demonstrated that hydrogen bonds HB‐II, HB‐III and HB‐IV are strengthened while hydrogen bond HB‐I is weakened in the four singly hydrogen‐bonded Res^?‐Water complexes upon photoexcitation. When the four hydrogen bonds are formed simultaneously between one resorufin anion and four water molecules in the Res^?‐4Water complex, all the hydrogen bonds are weakened in both the ground and excited states compared with those in the corresponding singly hydrogen‐bonded Res^?‐Water complexes. Furthermore, in complex Res^?‐4Water, hydrogen bonds HB‐II and HB‐IV are strengthened while hydrogen bonds HB‐I and HB‐III are weakened after the electronic excitation. The hydrogen bond strengthening and weakening in the various hydrogen‐bonded Res^?‐water complexes should be due to the redistribution of the charges among the four heteroatoms (O_1‐3 and N₁) within the resorufin molecule upon the optical excitation.     

The effect of intragranular microstress in A1203-SiC nanocomposites

A theoretical model is established to investigate the intragranular particle residual stress in A1203-SiC nanocom-posites. Using this model, we calculate the average compressive stress on the A1203 grain boundary （GB） and the average tensile stress within A1203 grains caused by SiC nanoparticles. The normal compressive stress strengthens the GB, and the average tensile stress weakens the grains. The model gives a reasonable interpretation of the strength changes of A1203-SiC nanocomposites with the number of SiC particles.     

On the variety of drastic transitions between solid phases

Parts of the author's conception regarding the variety of drastic transitions between solid phases were described in different previous papers. These parts are supplemented here and integrated into this paper.     

A TD-DFT study on the hydrogen bonding of three esculetin complexes in electronically excited states: strengthening and weakening

Time-dependent density functional theory (TD-DFT) method was used to study the excited-state hydrogen bonding of three esculetin complexes formed with aprotic solvents. The geometric structures, molecular orbitals (MOs), electronic spectra and the infrared (IR) spectra of the three doubly hydrogen-bonded complexes formed by esculetin and aprotic solvents dimethylsulfoxide (DMSO), tetrahyrofuran (THF) and acetonitrile (ACN) in both ground state S(0) and the first singlet excited state S(1) were calculated by the combined DFT and TD-DFT methods with the COSMO solvation model. Two intermolecular hydrogen bonds can be formed between esculetin and the aprotic solvent in each hydrogen-bonded complex. Based on the calculated bond lengths of the hydrogen bonds and the groups involved in the formation of the intermolecular hydrogen bonds in different electronic states, it is demonstrated that one of the two hydrogen bonds formed in each hydrogen-bonded complex is strengthened while the other one is weakened upon photoexcitation. Furthermore, it is found that the strength of the intermolecular hydrogen bonds formed in the three complexes becomes weaker as the solvents change from DMSO, via THF, to ACN, which is suggested to be due to the decrease of the hydrogen bond accepting (HBA) ability of the solvents. The spectral shifts of the calculated IR spectra further confirm the strengthening and weakening of the intermolecular hydrogen bonds upon the electronic excitation. The variations of the intermolecular hydrogen bond strengths in both S(0) and S(1) states are proposed to be the main reasons for the gradual spectral shifts in the absorption and fluorescence spectra both theoretically and experimentally.     

Experimental investigations on the weakening effect of magnetic fields on surface‐enhanced Raman scattering

Currently, because of the wide use of magnetic/metal hybrid materials in the field of surface‐enhanced Raman scattering (SERS), magnetic fields (MFs) as a kind of surrounding environments of SERS substrates have been not ignored. And enormous attentions for the effect of MFs on SERS are very necessary. Our analysis from previous reports shows SERS signals are closely associated with MFs; yet the study of the exact effect of MFs on SERS is still in need of detail and broadening. In this work, we demonstrate that the use of Ni/Au microparticles (MPs) and Au hollow spheres (HSs) to study the effect of MFs on SERS signals. The experiments are preformed from three aspects, including the comparison of SERS signals of Ni/Au MPs with different Ms values, the comparison of SERS signals of Au HSs and Ni/Au MPs under different external MFs, and the comparison of SERS signals of single Au HS particle and single Ni/Au particle in the absence and presence of an external MF. Thereinto, under different external MFs from 0, 0.01, 0.02, 0.04 to 0.08 T, SERS signals of Au HSs and Ni/Au MPs are gradually weaker. According to the experiments, the weakening effect of MFs on SERS is confirmed. It is suggested that the weakening effect is originated from the blue‐shift of surface plasmon resonance and the locking of charge‐transfer from Au to probe molecules. Copyright © 2012 John Wiley & Sons, Ltd.     

The parallel refinement of weakening idempotent pair

In this paper, we invent the parallel refinement, which refines the weakening idempotent pair into the positive and contractive one preserving K-theory information. We conduct a quantitative matrix analysis for this refinement, which shows that this refinement is more effective when we derive almost projection from weakening idempotent pairs.