An experimental and theoretical study of ring closing dynamics in HN3

Physical Chemistry Chemical Physics : PCCP
Jianyang ZhangAlec M Wodtke

Abstract

We report on an H(D)-atom Rydberg tagging experiment for H(D)N(3) photolysis providing detailed dynamical information on the wavelength dependence of the H(D) + N(3) channel. We observe subtle yet striking changes in the photochemical dynamics as the photolysis energy passes through approximately 5.6 eV. In addition to producing linear azide with an average of approximately 40% of available energy appearing as translation, a second H(D)-atom producing channel grows in above this energy releasing only about 15%. An observed (inverse) isotope effect suggests that statistical decomposition on S(0) is unimportant. High level ab initio quantum chemical calculations reveal a transition state to cyclization of the N(3) moiety in H(D)N(3) on the first excited singlet (S(1)) surface that is close in energy to the experimentally observed threshold energy for this "slow channel". Furthermore, the translational energy release of the "slow channel" is energetically consistent with cyclic-N(3) formation. This work provides the clearest presently available insights into how ring closure can occur in azide photochemistry.

References

Nov 20, 1996·Inorganic Chemistry·Mikhail N. GlukhovtsevPaul von Ragué Schleyer
Nov 25, 2003·Inorganic Chemistry·Lana Y BruneyDouglas L Strout
Jan 11, 2005·The Journal of Chemical Physics·Peng ZhangAlec M Wodtke
Mar 3, 2005·The Journal of Chemical Physics·Dmitri BabikovKeiji Morokuma
Aug 20, 2005·The Journal of Chemical Physics·Peter C SamartzisAlec M Wodtke
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Citations

Nov 9, 2010·The Journal of Chemical Physics·Dmitri Babikov, Brian K Kendrick
Feb 9, 2007·The Journal of Chemical Physics·Peter C SamartzisAlec M Wodtke
Dec 20, 2012·The Journal of Chemical Physics·B R L GalvãoA J C Varandas
Dec 21, 2006·The Journal of Chemical Physics·Scott J GoncherDaniel M Neumark
Jul 7, 2007·Physical Chemistry Chemical Physics : PCCP·Peter C Samartzis, Alec M Wodtke
Aug 2, 2006·Physical Chemistry Chemical Physics : PCCP·Peter C SamartzisAlec M Wodtke
Aug 16, 2017·The Journal of Chemical Physics·Alfredo Quinto-HernandezAlec M Wodtke
Jan 24, 2008·The Journal of Physical Chemistry. a·Christopher LarsonAlec M Wodtke
May 27, 2008·The Journal of Physical Chemistry. a·Kaijun YuanXueming Yang
Sep 21, 2011·The Journal of Physical Chemistry. a·B R L Galvão, A J C Varandas

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