共查询到20条相似文献,搜索用时 46 毫秒
1.
C4H5N-(H2O)n氢键团簇的多光子电离与从头计算研究 总被引:1,自引:0,他引:1
在355、532nm激光波长下用TOF质谱研究了C4H5N-(H2O)n氢键团簇体系的多光子电离。二波长下均得到一系列C4H5N-(H2O)n+及质子化产物C4H5N-(H2O)nH+。355nm下可能存在双光子共振电离过程,使得该波长下吡咯母体及团簇离子信号较532nm有明显增强。从头计算结果表明质子化产物的质子更可能连接于吡咯环的α-C原子,而不是N原子上,即光电离过程诱发了一个簇内的质子转移反应。在532nm下质子化产物的生成主要来自于一个发生于团簇内部的Penning电离或电荷转移过程。团簇的形成对吡咯光解产物的稳定化作用使得团簇系列C4H4N-(H2O)n+出现反常强度变化。 相似文献
2.
3.
4.
应用激光多光子电离质谱和分子束技术研究了氨和甲醇二元团簇,实验观测到两个系列质子化的团簇离子: (CH3OH)nH+和(CH3OH)nNH4+(1≤n≤14 ),其产生是经过二元团簇内的质子转移反应。同时也研究了氘代甲醇CH3OD和氨混合团簇,结果表明OD原子团中的D转移概率比CH3原子团中的质子转移概率大几倍。在HF/STO-3G和MP2/6-31G* *水平上对氨和甲醇二元团簇进行了计算,结果表明与CH3相比OH中的质子转移更加容易,因为CH3中的质子转移过程要克服高度约120 kJ/mol的能垒。 相似文献
5.
用355 nm激光对脉冲分子束超声膨胀冷却的甲醇分子进行多光子电离, 飞行时间质谱仪观测到除甲醇碎片离子外的质子化甲醇团簇(CH3OH)nH+(n=1-16), 且离子的种类及相对强度与激光相对于脉冲分子束的延时无关, 取决于团簇离子内在结构的稳定性. 结合从头算密度泛函理论, 在B3LYP/6-31G(d)基组水平上优化得到了(CH3OH)n和(CH3OH)nH+(n=1-4)的稳定构型. 振动频谱分析显示, 团簇中最强的红外振动模主要来自氢键H伸缩振动的贡献. 团簇电离后发生于团簇内的质子转移反应也可能与激光电离引起的与氢键有关的振动模激发密切相关. 相似文献
6.
The stable structures and vibrational spectra of protonated acetone molecule clusters with different sizes (CH3COCH3)nH +(n=1-7)are calculated at the 6-31G(d)level by means of density functional theory (B3LYP)quantum chemical calculations. The corresponding energies are analyzed at the level B3LYP/6-311+G(3df,2p)in order to obtain more accurate results. The proton affinity of neutral cyclic acetone molecule clusters increases with the increasing of cluster size. The calculated results show that the protonated acetone clusters have certain growth regularity with forming a solvation shell at the beginning and then new added acetone molecule attacking different active sites including the middle carbon atoms and the different methyl in solvation shell. The IR spectra of the protonated clusters are more complicate than that of neutral ones. The strongest peaks result from the movement of the proton between the two oxygen atoms in solvant shell apart from the case of n=1. Carbonyl stretching vibraional peaks split into the more and more and in general the corresponding intensities are weakened due to the protonation with the increasing of cluster size. 相似文献
7.
8.
9.
用同步辐射光源和光电离质谱研究了分子束中ArHClvanderWaals(vdW)团簇的光电离过程.测量结果表明,分子束中的ArHCl的浓匠与气源压力近似满足如下关系式:a(ArHCl)%=179×10-8.首次给出了ArHCl团簇的光电高效率曲线,并测得ArHCl 的出现势为12.52±0.03eV。根据实验测量的HCl和ArHCl的电高能,计算出Ar-HCl 的解高能为022±0.03eV.用Gaussian-94w量化程序计算出解高能约为0.16eV.实验表明当团簇内的Ar电离时,ArHCl 质谱峰强度明显低于预计的强度,是由于体系电离后发生了电荷转移及解离过程. 相似文献
10.
利用同步辐射和超声射流技术产生了团簇离子(CH_3CN)_m(C_2H_3Cl)(m≤4,n≤4)及C2H3ClCN+,C2H2ClCN+由(CH3CN)(C2H3Cl)+经团簇内离子。分子反应生成,反应过程中放出能量使H3C-CN键断裂。abinitio计算表明C2H3ClCN+离子是稳定的。同时测得了它们的电离势. 相似文献
11.
12.
Direct ab‐initio molecular dynamics study on the radiation effects on catalytic triad composed of Ser‐His‐Glu residues 下载免费PDF全文
High energy irradiation to the hydrogen bonded system is important in relevance with the initial process of DNA and enzyme damages. In the present study, the effects of radiation to catalytic triad have been investigated by means of direct ab‐initio molecular dynamics (AIMD) calculation. As a model of the catalytic triad, Ser‐His‐Glu residue, which is one of the important enzymes in the acylation reaction, was examined. The ionization and electron attachment processes in Ser‐His‐Glu were investigated as the radiation effects. The direct AIMD calculation showed that a proton of His is spontaneously transferred to carbonyl oxygen of Glu after the ionization. However, the whole structure of catalytic triad was essentially kept after the ionization. On the other hand, in the case of the electron capture in the model catalytic triad Ser‐His‐Glu, the dissociation of Glu residue from [Ser‐His]? was found as a product channel. The mechanism of ionization and electron capture process in the catalytic triad was discussed on the basis of theoretical results. © 2015 Wiley Periodicals, Inc. 相似文献
13.
14.
15.
Prof. Stefano Falcinelli Prof. Marzio Rosi Prof. Simonetta Cavalli Prof. Fernando Pirani Prof. Franco Vecchiocattivi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12518-12526
Focus in the present paper is on the analysis of total and partial ionization cross sections, measured in absolute value as a function of the collision energy, representative of the probability of ionic product formation in selected electronic states in Ne*?H2O, H2S, and NH3 collisions. In order to characterize the imaginary part of the optical potential, related to electronic couplings, we generalize a methodology to obtain direct information on the opacity function of these reactions. Such a methodology has been recently exploited to test the real part of the optical potential (S. Falcinelli et al., Chem. Eur. J., 2016 , 22, 764–771). Depending on the balance of noncovalent contributions, the real part controls the approach of neutral reactants, the removal of ionic products, and the structure of the transition state. Strength, range, and stereoselectivity of electronic couplings, triggering these and many other reactions, are directly obtained from the present investigation. 相似文献
16.
细胞色素c氧化酶研究新进展 总被引:13,自引:0,他引:13
综述了细胞色素c氧化酶研究的新进展,重点评述了细胞色素c氧化酶晶体结构和各种谱学研究结果,质子传递途径、O2还原的催化机理以及与其相耦联的质子泵机理等方面的最新进展。 相似文献
17.
Yajing Hu Albert Solé-Daura Dr. Yang-Rong Yao Xuechen Liu Dr. Sijie Liu Ao Yu Dr. Ping Peng Prof. Josep M. Poblet Dr. Antonio Rodríguez-Fortea Prof. Luis Echegoyen Prof. Fang-Fang Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1748-1753
The chemistry of cationic forms of clusterfullerenes remain less explored than that of the corresponding neutral or anionic species. In the present work, M3N@Ih-C80 (M=Sc or Lu) cations were generated by both electrochemical and chemical oxidation methods. The as-obtained cations successfully underwent the typical Bingel–Hirsch reaction that fails with neutral Sc3N@Ih-C80. Two isomeric Sc3N@Ih-C80 cation derivatives, [5,6]-open and [6,6]-open adducts, were synthesized, and the former has never been prepared by means of a Bingel–Hirsch reaction with neutral clusterfullerenes. In the case of the Lu3N@Ih-C80 cation, however, only a [6,6]-open adduct was obtained. Density functional theory (DFT) calculations indicated that the oxidized M3N@Ih-C80 was much more reactive than the neutral compound upon addition of the diethyl bromomalonate anion. The Bingel–Hirsch reaction of M3N@Ih-C80 cations occurred by means of an unusual outer-sphere single-electron transfer (SET) process from the diethyl bromomalonate anion to the stable intermediate [M3N@C80(C2H5COO)2CBr].. Remarkably, the diethyl bromomalonate anion was found to act as both a nucleophile and an electron donor. 相似文献
18.
19.
20.
Sebastian Preiß Ayla Päpcke Lukas Burkhardt Luca Großmann Prof. Dr. Stefan Lochbrunner Prof. Dr. Matthias Bauer Prof. Dr. Till Opatz Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(23):5940-5949
In the context of solar-to-chemical energy conversion, inspired by natural photosynthesis, the synthesis, electrochemical properties and photoinduced electron-transfer processes of three novel zinc(II)-gold(III) bis(porphyrin) dyads [ZnII(P)–AuIII(P)]+ are presented (P: tetraaryl porphyrin). Time-resolved spectroscopic studies indicated ultrafast dynamics (k >1010 s−1) after visible-light excitation, which finally yielded a charge-shifted state [ZnII(P ⋅ +)–AuII(P)]+ featuring a gold(II) center. The lifetime of this excited state is quite long due to a comparably slow charge recombination (k ≈3×108 s−1). The [ZnII(P ⋅ +)–AuII(P)]+ charge-shifted state is reductively quenched by amines in bimolecular reactions, yielding the neutral zinc(II)–gold(II) bis(porphyrin) ZnII(P)–AuII(P). The electronic nature of this key gold(II) intermediate, prepared by chemical or photochemical reduction, is elucidated by UV/Vis, X-band EPR, gold L3-edge X-ray absorption near edge structure (XANES) and paramagnetic 1H NMR spectroscopy as well as by quantum chemical calculations. Finally, the gold(II) site in ZnII(P)–AuII(P) is thermodynamically and kinetically competent to reduce an aryl azide to the corresponding aryl amine, paving the way to catalytic applications of gold(III) porphyrins in photoredox catalysis involving the gold(III/II) redox couple. 相似文献