Atomic scale KMC simulation of {100} oriented CVD diamond film growth under low substrate temperature-Part Ⅱ Simulation of CVD diamond film growth in C-H system and in Cl-containing systems

The growth of {100}-oriented CVD diamond film under two modifications ofJ-B-H model at low substrate temperatures was simulated by using a revised KMC method at atomicscale. The results were compared both in Cl-containing systems and in C-H system as follows: (1)Substrate temperature can produce an important effect both on film deposition rate and on surfaceroughness; (2) Aomic Cl takes an active role for the growth of diamond film at low temperatures; (3){100}-oriented diamond film cannot deposit under single carbon insertion mechanism, which disagreeswith the predictions before; (4) The explanation of the exact role of atomic Cl is not provided inthe simulation results.

Atomic scale KMC simulation of {100} oriented CVD diamond film growth under low substrate temperature—Part I Simulation of CVD diamond film growth under Joe-Badgwell-Hauge model

The growth of (100} oriented CVD (Chemical Vapor Deposition) diamond film under Joe-Badgwell-Hauge (J-B-H) model is simulated at atomic scale by using revised KMC (Kinetic Monte Carlo) method. The results show that: (1) under Joe's model, the growth mechanism from single carbon species is suitable for the growth of (100) oriented CVD diamond film in low temperature; (2) the deposition rate and surface roughness (Rq) under Joe's model are influenced intensively by temperature (Ta) and not evident bymass fraction W of atom chlorine; (3)the surface roughness increases with the deposition rate, i.e. the film quality becomes worse with elevated temperature, in agreement with Grujicic's prediction; (4) the simulation results cannot make sure the role of single carbon insertion.

Theoretical Study on Thermodynamic Properties and Hydrophilicity of Polychorinated Phenothiazines (PCPTZs)

The thermodynamic properties of 135 polychlorinated phenothiazines （PCPTZs） in the standard state are calculated using a combination of quantum mechanical computations performed with the Gaussian 03 program at the B3LYP/6-311G^＊＊ level, and their octanol-water partition coefficients （logKow） are calculated based on group contributions. The chlorine substitution pattern strongly influenced the thermodynamic properties and hydrophilicity of the compounds. The thermodynamic properties of congeners also depend on the chlorine substitution pattern. The effect of chlorine substitution pattern is quantitatively studied by considering the mmaber and position of Cl atom substitution （Npcs）. The results show that the Npcs model may be used to predict the thermodynamic properties and hydrophilicity for all 135 PCPTZ congeners.

Kinetic and product studies of Cl atoms reactions with a series of branched Ketones

The rate constants for the C1 atom reaction with three branched ketones have been measured at 298 ± 2 K and 760 Torr using the relative rate method in the absence of NO. The rate constants values obtained （in units of 10^-10 cm^3/（molecule.sec）） are： k（2-methyl-3-pentanone） = 1.07 ± 0.26, k（3-methyl-2-pentanone） =1.21 ± 0.26, and k（4-methyl-2-pentanone） = 1.35 ± 0.27. Combining the chemical kinetic data obtained by this study with those reported for other ketones, a revised Structure Activity Relationship （SAR） parameter and R group reactivity （kR of R（O）R＇ and CHx （x = 1, 2, 3） group reactivity （kCHx） toward C1 atoms were proposed. In addition, the products from the three reactions in the presence of NO were also identified and quantified by using PTR-ToF-MS and GC-FID, and the yields of the identified products are： acetone （39% ± 8%） ＋ ethanal （78% ± 12%）, 2-butanone （22% ± 2%） ＋ ethanal （75% ± 10%） ＋ propanal （14% ± 1%） and acetone （26% ± 3%） ＋ 2-methylpmpanal （24% ± 2%）, for C1 atoms reaction with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone, respectively. Based on the obtained results, the reaction mechanisms of C1 atoms with these three ketones are proposed.

Study on the reaction of 3-methyl-2-butenal and 3-methylbutanal with Cl atoms: kinetics and reaction mechanism

The reaction of Cl atoms with two C5aldehydes(3-methyl-2-butenal and 3-methylbutanal)were investigated by proton-transfer-reaction mass spectrum(PTR-MS)using smog chamber at 298±1 K and 760 Torr.A relative rate method was used to determine the rate constants of the title reactions with m-xylene and trans-2-butene as reference compounds:(3.04±0.18)×10^(-10)and(2.07±0.14)×10^(-10)cm^(3)/(molecule·sec)for 3-methyl-2-butenal and 3-methylbutanal,respectively.Additionally,the gas-phase products were also identified by PTR-MS,and the possible reaction mechanisms were proposed basing on the identified products.The detected gas-phase products are similar for two C5aldehydes reactions,mainly including small molecules of aldehydes,ketones and chlorinated aldehyde compounds.The atmospheric lifetimes(τ)calculated for 3-methyl-2-butenal(τ=7.0 hr,marine boundary layer(MBL))and 3-methylbutanal(τ=10.3 hr,MBL)according to the obtained rate constants.The results indicate that Cl atoms at MBL are competitive with OH radicals for the degradation contribution of C5aldehyde compounds.