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The B$^2Pi-$X$^2Pi$ electronic origin band of $^{13}$C$_6$H

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 نشر من قبل Xavier Bacalla
 تاريخ النشر 2015
  مجال البحث فيزياء
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The rotationally resolved spectrum of the B$^2Pi-$X$^2Pi$ electronic origin band transition of $^{13}$C$_6$H is presented. The spectrum is recorded using cavity ring-down spectroscopy in combination with supersonic plasma jets by discharging a $^{13}$C$_2$H$_2$/He/Ar gas mixture. A detailed analysis of more than a hundred fully-resolved transitions allows for an accurate determination of the spectroscopic parameters for both the ground and electronically excited state of $^{13}$C$_6$H.

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Electronic spectra of C$_6$H are measured in the $18,950-21,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manif old of the B$^2Pi$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $ u_6$ mode associated with the C-C bond vibration and the $ u_4$ and $ u_3$ modes associated with C$equiv$C triple bonds. For the two lowest $ u_{11}$ and $ u_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $mu^2Sigma$($ u_{11}$) and both $mu^2Sigma$($ u_{10}$) and $kappa^2Sigma$($ u_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $mu^2Sigma$($ u_9$) and $mu^2Sigma$($ u_8$) levels. In the excitation region below the first non-degenerate vibration ($ u_6$), some $^2Pi-^{2}Pi$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2Pi-^{2}Pi$ transition found above the $ u_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2Pi$ state of C$_6$H is derived and presented.
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