Reaction dynamics on the formation of 1- and 3-cyanopropylene in the crossed beams reaction of ground-state cyano radicals (CN) with propylene (C3H6) and its deuterated isotopologues.

نویسندگان

  • Xibin Gu
  • Fangtong Zhang
  • Ralf I Kaiser
چکیده

Crossed molecular beams experiments were utilized to explore the chemical reaction dynamics of ground-state cyano radicals, CN(X(2)Sigma(+)), with propylene (CH3CHCH2) together with two d3-isotopologues (CD3CHCH2, CH3CDCD2) as potential pathways to form organic nitriles under single collision conditions in the atmosphere of Saturn's moon Titan and in the interstellar medium. On the basis of the center-of-mass translational and angular distributions, the reaction dynamics were deduced to be indirect and commenced via an addition of the electrophilic cyano radical with its radical center to the alpha-carbon atom of the propylene molecule yielding a doublet radical intermediate: CH3CHCH2CN. Crossed beam experiments with propylene-1,1,2-d3 (CH3CDCD2) and propylene-3,3,3-d3 (CD3CHCH2) indicated that the reaction intermediates CH3CDCD2CN (from propylene-1,1,2-d3) and CD3CHCH2CN (from propylene-3,3,3-d3) eject both atomic hydrogen through tight exit transition states located about 40-50 kJ mol(-1) above the separated products: 3-butenenitrile [H2CCDCD2CN] (25%), and cis/trans-2-butenenitrile [CD3CHCHCN] (75%), respectively, plus atomic hydrogen. Applications of our results to the chemical processing of cold molecular clouds like TMC-1 and OMC-1 are also presented.

برای دانلود رایگان متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Reaction dynamics of phenyl radicals (C6H5) with propylene (CH3CHCH2) and its deuterated isotopologues.

The reactions between phenyl radicals (C6H5) and propylene (CH3CHCH2) together with its D6- and two D3-isotopologues were studied under single collision conditions using the crossed molecular beams technique. The chemical dynamics inferred from the center-of-mass translational and angular distributions suggests that the reactions are indirect and initiated by an addition of the phenyl radical t...

متن کامل

A crossed molecular beams study of the reaction of the ethynyl radical ( C 2 H ( X 2 R + ) ) with allene ( H 2 CCCH 2 ( X 1 A 1 ) )

The crossed beams reaction of ground state ethynyl radicals, C2H(X S), with allene, H2CCCH2(X A1), was conducted under single collision conditions at a collision energy of 22.0 0.4 kJ mol. The center-of-mass functions were combined with earlier ab initio calculations and revealed that the reaction was barrier-less, proceeded via indirect reaction dynamics through an addition of the ethynyl radi...

متن کامل

Crossed beam reaction of cyano radicals with hydrocarbon molecules . II . Chemical dynamics of 1 - cyano - 1 - methylallene „ CNCH 3 CCCH 2 ; X 1 A 8 ... formation from reaction

Crossed beam reaction of cyano radicals with hydrocarbon molecules. II. Chemical dynamics of 1-cyano-1-methylallene „CNCH3CCCH2; X A8... formation from reaction of CN„X 2S1... with dimethylacetylene CH3CCCH3 „X A18... N. Balucani, O. Asvany, A. H. H. Chang, S. H. Lin, Y. T. Lee, and R. I. Kaiser Institute of Atomic and Molecular Sciences, 1, Section 4, Roosevelt Road, 107 Taipei, Taiwan, Republ...

متن کامل

Crossed molecular beams study on the formation of vinylacetylene in Titan's atmosphere.

The reaction of ground-state ethynyl radicals, C(2)H(X(2)Sigma(+)), with d(4)-ethylene, C(2)D(4)(X(1)A(g)), was investigated at a collision energy of 20.6 +/- 0.4 kJ mol(-1) utilizing the crossed-beams technique. Combined with electronic structure calculations, our results elucidate that this reaction follows indirect reaction dynamics via a doublet radical complex. The reaction is initiated by...

متن کامل

Crossed beam reaction of cyano radicals with hydrocarbon molecules . II . Chemical dynamics of 1 - cyano - 1 - methylallene „ CNCH 3 CCCH 2 ; X 1 A 8 ... formation from reaction of CN „ X

Crossed beam reaction of cyano radicals with hydrocarbon molecules. II. Chemical dynamics of 1-cyano-1-methylallene „CNCH3CCCH2; X A8... formation from reaction of CN„X 2S1... with dimethylacetylene CH3CCCH3 „X A18... N. Balucani, O. Asvany, A. H. H. Chang, S. H. Lin, Y. T. Lee, and R. I. Kaiser Institute of Atomic and Molecular Sciences, 1, Section 4, Roosevelt Road, 107 Taipei, Taiwan, Republ...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

عنوان ژورنال:
  • The journal of physical chemistry. A

دوره 112 39  شماره 

صفحات  -

تاریخ انتشار 2008