【摘要】：燃燒在日常生活中起著不可替代的作用。目前,世界上大約90%的能量都是由燃燒生成的。燃燒的應用十分廣泛,幾乎所有人類所需要的動力生產(chǎn),都涉及到燃料的燃燒。在人類所需的動力生產(chǎn)中,發(fā)動機是燃料燃燒產(chǎn)生能量的一種重要熱能動力裝置。發(fā)動機內(nèi)燃料燃燒的本質(zhì)是化學反應。因此,對于燃料燃燒的化學反應動力學過程的研究,對提高燃燒效率、降低污染物排放以及尋找替代燃料等具有重要意義。而在發(fā)動機燃料燃燒過程中,燃料高溫裂解過程是十分重要的。對于其化學反應動力學過程的研究,將有利于霧化質(zhì)量的改善,空氣的供給量、點火區(qū)域和燃燒室溫度的控制。作為化學動力學的重要參數(shù),化學反應速率常數(shù)是燃燒化學中的一項重要科學數(shù)據(jù)。此外,非諧振效應在單分子解離,尤其是在團簇分子中的重要性日益顯著。本論文根據(jù)RRKM (Rice-Ramsperger-Kassel-Marcus)理論,用YL方法分別計算了單分子反應體系M2+(H2O)2(M=Be, Mg, Ca), CF3XCF2CH3(X=Cl,Br)和 CF3XCF2CD3(X=Cl, B r), CH3OOH 和 CD3OOD, CH2OHCH2OH, CH2OHCHOHCH2OH 和 CH3OCH3的速率常數(shù),并且對反應體系的非諧振效應進行了研究。首先,用Gaussian03軟件在MP2/6-311G(d,p), B3LYP/6-311++G(d,p), MP2/6-311++G(3df,3pd) , MP2/6-311++G(d,p) , MP2/6-311G(d,p)和MP2/6-311++G(3df,3pd)水平上分別對上述單分子反應體系的所有反應物和過渡態(tài)的構(gòu)型進行優(yōu)化,進而得到各個構(gòu)型的簡諧和非諧振振動頻率。其次,用CCSD(T)或 CBS-QB3方法對優(yōu)化后構(gòu)型的單點能重新進行計算,該值經(jīng)零點能修正后,繼而得到各個單分子反應的勢壘。最后,計算得出各個單分子反應的微正則系綜總態(tài)數(shù)、態(tài)密度、速率常數(shù)以及正則系綜速率常數(shù)。結(jié)果顯示：(1)反應的速率常數(shù)隨著系統(tǒng)溫度的增加而增加,但其增長率卻逐漸減小。(2)對于反應物分子結(jié)構(gòu)相似的單分子解離反應而言,反應物分子的對稱性越好,反應的非諧振效應越小。(3)在反應物分子D代情況下,反應體系的非諧振效應發(fā)生變化,也就是說同位素效應對于非諧振效應具有一定的影響。
[Abstract]:Combustion plays an irreplaceable role in daily life. Currently, about 90% of the world's energy is generated by combustion. Combustion is widely used, almost all the power production human needs, involving the combustion of fuel. The engine is an important thermal power device for generating energy from fuel combustion in the power production required by human beings. The essence of fuel combustion in an engine is chemical reaction. Therefore, the study of chemical reaction kinetics of fuel combustion is of great significance to improve combustion efficiency, reduce pollutant emissions and find alternative fuels. In the process of engine fuel combustion, the high temperature pyrolysis process is very important. The study of chemical reaction kinetics will be beneficial to the improvement of atomization quality, air supply, ignition area and combustion chamber temperature control. As an important parameter of chemical kinetics, chemical reaction rate constant is an important scientific data in combustion chemistry. In addition, the non-resonance effect is becoming more and more important in the dissociation of monolayers, especially in cluster molecules. Based on the RRKM (Rice-Ramsperger-Kassel-Marcus) theory, the rate constants of M _ 2 (H _ 2O) _ 2 (MRRKM, Mg, Ca), CF3XCF2CH3 (Mg, Ca), CF3XCF2CH3) and CF3XCF2CD3 (X _ nCl _ l, B r), CH3OOH, CD3OOD, CH2OHCH2OH, CH2OHCHOHCH2OH and CH3OCH3) have been calculated by YL method, respectively. The non-resonance effect of the reaction system is also studied. First of all, using Gaussian03 software in MP2/6-311G (DNP), B3LYP/6-311 G (dapp), MP2/6-311 G (3dfU 3pd), MP2/6-311 G (dapp), MP2/6-311G (dapp) and MP2/6-311 G (3df. The configurations of all the reactants and transition states are optimized at the 3pd level, and the harmonic and non-resonant vibration frequencies of each configuration are obtained. Secondly, the single point energy of the optimized configuration is recalculated by CCSD (T) or CBS-QB3 method. After the zero energy is corrected, the potential barriers of each monolayer reaction are obtained. Finally, the total number of states, the density of states, the rate constant and the regular ensemble rate constant of each monolayer reaction are calculated. The results show that: (1) the rate constant of the reaction increases with the increase of the system temperature, but the growth rate decreases gradually. (2) for the monolayer dissociation reaction with similar molecular structure, the better the symmetry of the reactant molecule is. (3) in the case of D generation of reactants, the non-resonance effect of the reaction system changes, that is to say, the isotope effect has a certain influence on the non-resonant effect.
【學位授予單位】：大連海事大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：TK401

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本文編號：2305253