Direct ab initio dynamics study on the rate constants and kinetic isotope effect for the reactions of H atoms with GeDn(CH3)4-n (n = 1-4)

Direct ab initio dynamics study on the rate constants and kinetic isotope effect for the reactions of H atoms with GeDn(CH3)4-n (n = 1-4)

Copyright 2002 Wiley Periodicals, Inc.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 23(2002), 14 vom: 15. Nov., Seite 1366-74
1. Verfasser: Wu, Yang (VerfasserIn)
Weitere Verfasser: Ding, Yi-Hong, Xiao, Jing-Fa, Li, Ze-Sheng, Huang, Xu-Ri, Sun, Chia-Chung
Format: Aufsatz
Sprache:English
Veröffentlicht: 2002
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article
LEADER 01000naa a22002652 4500
001 NLM120729687
003 DE-627
005 20231222191518.0
007 tu
008 231222s2002 xx ||||| 00| ||eng c
028 5 2 |a pubmed24n0403.xml 
035 |a (DE-627)NLM120729687 
035 |a (NLM)12214319 
040 |a DE-627  |b ger  |c DE-627  |e rakwb 
041 |a eng 
100 1 |a Wu, Yang  |e verfasserin  |4 aut 
245 1 0 |a Direct ab initio dynamics study on the rate constants and kinetic isotope effect for the reactions of H atoms with GeDn(CH3)4-n (n = 1-4) 
264 1 |c 2002 
336 |a Text  |b txt  |2 rdacontent 
337 |a ohne Hilfsmittel zu benutzen  |b n  |2 rdamedia 
338 |a Band  |b nc  |2 rdacarrier 
500 |a Date Completed 20.03.2003 
500 |a Date Revised 03.11.2003 
500 |a published: Print 
500 |a Citation Status PubMed-not-MEDLINE 
520 |a Copyright 2002 Wiley Periodicals, Inc. 
520 |a Direct ab initio dynamic calculations are performed on the reactions of atomic hydrogen with GeD(n)(CH(3))(4-n) (n = 1-4) over the temperature range 200-2000 K at the PMP4SDTQ/6-311 +G(3df,2p)//MP2/6-31 +G(d) (for n = 2-4) and G2//MP2/6-31 +G(d) (for n = 1) levels. The corresponding k(H)/k(D) ratios are then calculated in order to determine the kinetic isotope effect for the four reactions. For the simplest GeD(4) +H reaction, the only one that has available experimental data, the calculated canonical variational transition state theory incorporates small-curvature tunneling correction (CVT/SCT) thermal rate constants, and the k(H)/k(D) values are in good agreement with the experimental values within the experimental temperature range 293-550 K. For the four GeD(n)(CH(3))(4-4) (n = 1-4) reactions, the variational effect is small over the whole temperature range, whereas the small-curvature effect is important in the lower temperature range. Finally, the overall rate constants are fitted to the three-parameter expression over the whole temperature range 200-2000 K as 5.8 x 10(8)T(1.68)exp(-929/T), 1.7 x 10(8)T(1.80)exp(-691/T), 2.58 x 10(8)T(1.71)exp(-706/T), and 1.0 x 10(7)T(2.08)exp(-544/T) cm(3) mol(-1) s(-1) for the n = 4, 3, 2, and 1 reactions. Our work may represent the first theoretical study of the kinetic isotope effect for the H-attack on the G-H bonding 
650 4 |a Journal Article 
700 1 |a Ding, Yi-Hong  |e verfasserin  |4 aut 
700 1 |a Xiao, Jing-Fa  |e verfasserin  |4 aut 
700 1 |a Li, Ze-Sheng  |e verfasserin  |4 aut 
700 1 |a Huang, Xu-Ri  |e verfasserin  |4 aut 
700 1 |a Sun, Chia-Chung  |e verfasserin  |4 aut 
773 0 8 |i Enthalten in  |t Journal of computational chemistry  |d 1984  |g 23(2002), 14 vom: 15. Nov., Seite 1366-74  |w (DE-627)NLM098138448  |x 1096-987X  |7 nnns 
773 1 8 |g volume:23  |g year:2002  |g number:14  |g day:15  |g month:11  |g pages:1366-74 
912 |a GBV_USEFLAG_A 
912 |a SYSFLAG_A 
912 |a GBV_NLM 
912 |a GBV_ILN_350 
951 |a AR 
952 |d 23  |j 2002  |e 14  |b 15  |c 11  |h 1366-74