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Register a new userThe B$^2Pi-$X$^2Pi$ electronic origin band of $^{13}$C$_6$H
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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 manifold 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.
Rotationally resolved spectra of the C$^2Sigma^+$-X$^2Pi$ electronic system of the CH radical were measured using cavity ring-down spectroscopy in supersonically expanding, planar hydrocarbon plasma. The experimental conditions allowed the study of highly excited rotational levels starting from vibrationally excited states. Here we present some 200+ new or more accurately recorded transitions in the 0-0, 1-1 and 2-2 vibronic bands in the ultraviolet between 30900-32400 cm$^{-1}$ (324-309 nm). The resulting data, compared to earlier measurements, allows for the determination of more precise molecular constants for each vibrational state and therefore more precise equilibrium values. From this an equilibrium bond length of 1.115798(17) r{A} for the C$^2{Sigma}^+$ state is determined. A comprehensive list with observed transitions for each band has been compiled from all available experimental studies and constraints are placed on the predissociation lifetimes.
We present detailed calculations on resonances in rotationally and spin-orbit inelastic scattering of OH ($X,^2Pi, j=3/2, F_1, f$) radicals with He and Ne atoms. We calculate new emph{ab initio} potential energy surfaces for OH-He, and the cross sections derived from these surfaces compare favorably with the recent crossed beam scattering experiment of Kirste emph{et al.} [Phys. Rev. A textbf{82}, 042717 (2010)]. We identify both shape and Feshbach resonances in the integral and differential state-to-state scattering cross sections, and we discuss the prospects for experimentally observing scattering resonances using Stark decelerated beams of OH radicals.
We use accurate quantum mechanical calculations to analyze the effects of parallel electric and magnetic fields on collision dynamics of OH(2Pi) molecules. It is demonstrated that spin relaxation in 3He-OH collisions at temperatures below 0.01 K can be effectively suppressed by moderate electric fields of order 10 kV/cm. We show that electric fields can be used to manipulate Feshbach resonances in collisions of cold molecules. Our results can be verified in experiments with OH molecules in Stark decelerated molecular beams and electromagnetic traps.
We report on the observation of magnetic dipole allowed transitions in the well-characterized $A,^2Sigma^+ - X,^2Pi$ band system of the OH radical. A Stark decelerator in combination with microwave Rabi spectroscopy is used to control the populations in selected hyperfine levels of both $Lambda$-doublet components of the $X,^2Pi_{3/2},v=0,J=3/2$ ground state. Theoretical calculations presented in this paper predict that the magnetic dipole transitions in the $ u=1 leftarrow u=0$ band are weaker than the electric dipole transitions by a factor of $2.58times 10^3$ only, i.e., much less than commonly believed. Our experimental data confirm this prediction.
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