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Theoretical Investigations on the Mechanisms for the Reactions of N_mO_n(m,n=1,2) Molecules with Several Important Radicals

Author: WeiZhiGang
Tutor: SunJiaZhong
School: Jilin University
Course: Physical and chemical
Keywords: Reaction channels Potential energy surface Radical reactions B3LYP/6-311G Oxynitride Doublet Reaction Mechanism Transition state Reaction intermediates Theoretical study
CLC: O621.2
Type: PhD thesis
Year: 2004
Downloads: 326
Quote: 0
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Abstract


Nitrogen oxide as the major air pollutants released by the combustion of fossil fuels, has been subject to extensive attention of chemists. Small free radicals to eliminate nitrogen oxides is important in atmospheric chemistry and combustion chemistry active topics at the forefront. In this thesis, the use of a high level of quantum chemistry calculation method system of nitrogen oxides and several important free radical reaction the reaction potential energy surface of a theoretical study, which include: 3C2 + NO reaction potential energy surface 3C2 + NO2 reaction potential energy surface, NCO + NO2 reaction potential energy surface. NCS + NO2 reaction potential energy surface, C2H + NO2 reaction potential energy surface, HCCN + NO reaction potential energy surface, C2N + NO reaction potential energy surface and CN + N2O reaction potential energy surface, through the theoretical analysis given reaction may produce the intermediates and transition states of the structure and energy, the possible reaction channels The reaction mechanism and the main product, provide a reference for further experimental studies. Mainly be summarized as follows: 1. Reaction potential energy surface of the reaction of C2 + 3NO doublet and quartet state CCSD (T) / 6-311G (d) / / B3LYP/6-311G (d) level research. Doublet potential energy surface contains six kinds of reaction intermediates, nine kinds of transition states, four products, and 11 reaction channels; quadruple the potential energy surface contains four kinds of reaction intermediates, transition states, three kinds of product and three reaction channel. By analyzing more competitive reaction channel for the dual trend can surface in the four reaction channels, respectively, as: Path RP1 (1): 1 CCNO R C2 NO → → 2 (NC) CO → 3 CNCO → P1 CN CO 3 Path RP1 (2): R → 1 → 4 CC (NO) → 2 → 3 → P1 CN CO Path RP2 (1): R → 1 → P2 O 2CCN 3 Path RP3 (1): R → 1 → 5 ON ( CC) → P3 O 2CCNring 3 at lower temperatures (T <968 K) strong competitive the reaction passage RP1 (1) and RP1 (2), the reaction product of P1 CN CO as the main product; at higher temperatures ( T gt; 3000 K), the reaction channel RP2 (1) I lt; WP = 192 gt; Abstract and RP3 (1), are highly competitive, in product P2 O 2CCN and P3 O 2CCNring as the main product. 332 G2 (B3LYP/MP2/CC) / / B3LYP/6-311G (d) level, the reaction C2 + a 3NO2 two doublet and quartet state potential energy surface. Doublet potential energy surface contains four kinds of reaction intermediates, nine kinds of transition states, four products and five reaction channels; the quadruple potential energy face in this reaction is not important, only a brief introduction. By analyzing more competitive reaction channel for the dual trend can surface in the four reaction channels, respectively, as: Path RP1 (1): R C2 NO2 → 1 CCN (O) O → of 2 OCCNO → P1 CO CNO 3 Path RP2 (1): R → 1 → 2 → 3 OC (O) CN → P2 CO2 CN Path RP3 (1): R → 1 → 2 → 3 OC (O) CN → P3 CO NCO Path RP3 (2): R → The pros and cons of the order of 1 → 2 → 4 OCC (O) N → P3 CO NCO four reaction channels for the reaction channels RP1 (1) better than the reaction channel RP2 (1) reaction channel RP2 (1) better than the reaction channel RP3 (1 ) reaction channel RP3 (1) is better than the the reaction channel RP3 (2). Gaussian-3 / / MP2/6-311G (d) level study the reaction NCO + NO2 the singlet and triplet state potential energy surface. Singlet potential energy surface contains four kinds of reaction intermediates, transition state, two kinds of product and two reaction channels; triplet potential energy to face this reaction is not important, only a brief introduction. For singlet posture by analyzing the comparison there is the competitiveness of the reaction channel can surface in the reaction channel RP1 (1) and RP2 (1), respectively: Path RP1 (1): R NCO NO2 → 1 O (O) NNCO → 2 the ON (NC (O) O) → P1NNO CO2 Path RP2 (1): R → 3 cis-trans-ONONCO → 4 cis-cis-ONONCO → P2CO 2NORP1 (1) as the main reaction pass RP2 (1) for the secondary reaction channel. HL / / MP2/6-311G (d) level study reaction NCS + NO2 singlet and triplet potential energy surface. Singlet potential energy surface contains four kinds of reaction intermediates, transition state, three kinds of product and three reaction channels; triplet potential energy to face this reaction is not important, only a brief introduction. Through analysis, comparison with competitive reaction channel can be expressed as: Path RP1 (1): R NCS NO2 → 1 O (O) NNCS → 2 ON (NC (S) O) → P1NNO OCSII lt; WP = 193 gt; Jilin University Doctoral Dissertation Path RP2 (1): R NCS NO2 → 3 O (O) NSCN → P2 ONS OCN reaction channel RP1 (1) of NCS NO2 reaction channel for reaction, the reaction channel RP2 (1) as the secondary reaction channel. Studied at the CCSD (T) / 6-311G (d, p) / / B3LYP/6-311G (d, p) level reaction C2H + NO2 singlet potential energy surface. Reactants were obtained from 27 kinds of reaction intermediates and 46 transition state, and six kinds of product by 26 reaction channels. More competitive reaction channels can be expressed as follows: Path RP1 (1): R C2H NO2 → 1 HCCN (O) O → 2 ON (O) C (H) C → 3trans-OCC (H) NO → P1 HCCO NO Path RP1 (2): R → 1 → 2 → 3 → 4 cis-OCC (H) NO → P1 Path RP1 (3): R → 6 HCCONO → P1 Path RP2 (1): R → 1 → 2 → 3 → P2 HCNO CO Path RP2 (2): R → 1 → 2 → 3 → 4 → P2 Path RP3 (1): R → 1 → 2 → 3 → 4 → 5 O (CONC) H → P3 HCN CO2 wherein reaction channels RP1 (1) and RP1 (2) as the main reaction channel the reaction channel RP2, (1), the RP2 (2) and RP3 (1), as a secondary reaction channel. The reaction passage RP1 (3) is one of the high temperature when the main reaction passage. CCSD (T) / 6-311G (d, p) / / B3LYP/6-311G (d, p) level to study the reaction HCCN NO doublet and quartet state potential energy surface. Doublet potential energy surface

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