TY - JOUR
T1 - Detection of the excited-State NH2 (Ã 2A1) in the ultraviolet photodissociation of methylamine
AU - Onitsuka, Yuuki
AU - Yamasaki, Katsuyoshi
AU - Goto, Hiroki
AU - Kohguchi, Hiroshi
N1 - Funding Information:
This work is supported by JSPS KAKENHI Grant No. 15KT0065. The authors are also grateful to Toray Research Fund for Science and Technology for their financial support.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/11/3
Y1 - 2016/11/3
N2 - Ion-imaging and dispersed fluorescence spectroscopy are employed for the photodissociation dynamics study of methylamine in the photolysis wavelength range 205−213 nm. The methyl radical product is found to populate a wide range of ro-vibrational States, among which the CH3 fragment generated in the v = 0 state shows a bimodal kinetic energy distribution. The internal energy analysis of the NH2 counterproduct indicates that a lower kinetic energy component, which was observed only with the CH3(v=0) fragment, energetically matches the electronically excited Ã2A1 state. The dispersed fluorescence spectrum, whose band structure is assigned to the Ã2A1 → X2B1 transition, provides evidence of the CH3(v=0) + NH2(Ã2A1) pathway. The branching mechanism of the product pathway is discussed in terms of nuclear dynamics in the long-range region, where the conical intersection between the excited- and ground-state potential energy surfaces can play a significant role.
AB - Ion-imaging and dispersed fluorescence spectroscopy are employed for the photodissociation dynamics study of methylamine in the photolysis wavelength range 205−213 nm. The methyl radical product is found to populate a wide range of ro-vibrational States, among which the CH3 fragment generated in the v = 0 state shows a bimodal kinetic energy distribution. The internal energy analysis of the NH2 counterproduct indicates that a lower kinetic energy component, which was observed only with the CH3(v=0) fragment, energetically matches the electronically excited Ã2A1 state. The dispersed fluorescence spectrum, whose band structure is assigned to the Ã2A1 → X2B1 transition, provides evidence of the CH3(v=0) + NH2(Ã2A1) pathway. The branching mechanism of the product pathway is discussed in terms of nuclear dynamics in the long-range region, where the conical intersection between the excited- and ground-state potential energy surfaces can play a significant role.
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U2 - 10.1021/acs.jpca.6b08674
DO - 10.1021/acs.jpca.6b08674
M3 - Article
AN - SCOPUS:85045857356
SN - 1089-5639
VL - 120
SP - 8584
EP - 8589
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 43
ER -