Far-UV photochemical bond cleavage of n-amyl nitrite: bypassing a repulsive surface

Michael P. Minitti; Yao Zhang; Martin Rosenberg; Rasmus Yding Brogaard; Sanghamitra Deb; Theis Ivan Sølling; Peter M. Weber

doi:10.1021/jp209727g

Far-UV photochemical bond cleavage of n-amyl nitrite: bypassing a repulsive surface

Michael P. Minitti, Yao Zhang, Martin Rosenberg, Rasmus Yding Brogaard, Sanghamitra Deb, Theis Ivan Sølling, Peter M. Weber

Department of Chemistry

2 Citations (Scopus)

Abstract

We have investigated the deep-UV photoinduced, homolytic bond cleavage of amyl nitrite to form NO and pentoxy radicals. One-color multiphoton ionization with ultrashort laser pulses through the S₂ state resonance gives rise to photoelectron spectra that reflect ionization from the S₁ state. Time-resolved pump-probe photoionization measurements show that upon excitation at 207 nm, the generation of NO in the v = 2 state is delayed, with a rise time of 283 (16) fs. The time-resolved mass spectrum shows the NO to be expelled with a kinetic energy of 1.0 eV, which is consistent with dissociation on the S₁ state potential energy surface. Combined, these observations show that the first step of the dissociation reaction involves an internal conversion from the S₂ to the S₁ state, which is followed by the ejection of the NO radical on the predissociative S₁ state potential energy surface.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	116
Issue number	2
Pages (from-to)	810-819
Number of pages	10
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp209727g
Publication status	Published - 19 Jan 2012

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Far-UV photochemical bond cleavage of n-amyl nitrite : bypassing a repulsive surface. / Minitti, Michael P.; Zhang, Yao; Rosenberg, Martin et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 116, No. 2, 19.01.2012, p. 810-819.

Research output: Contribution to journal › Journal article › Research › peer-review

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title = "Far-UV photochemical bond cleavage of n-amyl nitrite: bypassing a repulsive surface",

abstract = "We have investigated the deep-UV photoinduced, homolytic bond cleavage of amyl nitrite to form NO and pentoxy radicals. One-color multiphoton ionization with ultrashort laser pulses through the S2 state resonance gives rise to photoelectron spectra that reflect ionization from the S1 state. Time-resolved pump-probe photoionization measurements show that upon excitation at 207 nm, the generation of NO in the v = 2 state is delayed, with a rise time of 283 (16) fs. The time-resolved mass spectrum shows the NO to be expelled with a kinetic energy of 1.0 eV, which is consistent with dissociation on the S1 state potential energy surface. Combined, these observations show that the first step of the dissociation reaction involves an internal conversion from the S2 to the S1 state, which is followed by the ejection of the NO radical on the predissociative S1 state potential energy surface.",

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AU - Minitti, Michael P.

AU - Zhang, Yao

AU - Rosenberg, Martin

AU - Brogaard, Rasmus Yding

AU - Deb, Sanghamitra

AU - Sølling, Theis Ivan

AU - Weber, Peter M.

PY - 2012/1/19

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N2 - We have investigated the deep-UV photoinduced, homolytic bond cleavage of amyl nitrite to form NO and pentoxy radicals. One-color multiphoton ionization with ultrashort laser pulses through the S2 state resonance gives rise to photoelectron spectra that reflect ionization from the S1 state. Time-resolved pump-probe photoionization measurements show that upon excitation at 207 nm, the generation of NO in the v = 2 state is delayed, with a rise time of 283 (16) fs. The time-resolved mass spectrum shows the NO to be expelled with a kinetic energy of 1.0 eV, which is consistent with dissociation on the S1 state potential energy surface. Combined, these observations show that the first step of the dissociation reaction involves an internal conversion from the S2 to the S1 state, which is followed by the ejection of the NO radical on the predissociative S1 state potential energy surface.

AB - We have investigated the deep-UV photoinduced, homolytic bond cleavage of amyl nitrite to form NO and pentoxy radicals. One-color multiphoton ionization with ultrashort laser pulses through the S2 state resonance gives rise to photoelectron spectra that reflect ionization from the S1 state. Time-resolved pump-probe photoionization measurements show that upon excitation at 207 nm, the generation of NO in the v = 2 state is delayed, with a rise time of 283 (16) fs. The time-resolved mass spectrum shows the NO to be expelled with a kinetic energy of 1.0 eV, which is consistent with dissociation on the S1 state potential energy surface. Combined, these observations show that the first step of the dissociation reaction involves an internal conversion from the S2 to the S1 state, which is followed by the ejection of the NO radical on the predissociative S1 state potential energy surface.

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JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

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ER -

Far-UV photochemical bond cleavage of n-amyl nitrite: bypassing a repulsive surface

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