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33745123019
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note
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Imidazole, pyrrole, and phenol were obtained commercially (Aldrich, Gillingham, UK, 98%). Pyrrole, at its room temperature vapor pressure (∼11 torr) and diluted in 700 torr of Ar, was introduced into the photolysis region in the form of a pulsed, skimmed molecular beam. For imidazole and phenol, solid samples were packed in the tube leading to the same pulsed molecular beam source and heated to ∼100°C (imidazole) or 60°C (phenol), and the resulting vapor entrained in 700 torr of Ar before expansion into the interaction region.
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33745171491
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note
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R = 67.07 dalton, 66.08 dalton, and 93.11 dalton), d = 0.368 m is the length of the flight path, and t is the measured H atom TOF.
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7
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33745135831
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note
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2 - 1)/2 is the second-order Legendre polynomial, β takes limiting values of +2 in the case of prompt dissociation after excitation via a parallel transition (i.e., μ lies along the breaking bond) and -1 in the case of a perpendicular transition. Less anisotropic fragment recoil distributions (i.e., with β closer to 0) are observed in the case of predissociations (i.e., where the excited state lifetime is comparable to, or longer than, the rotational period of the parent molecule).
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9
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33745122681
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note
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Equilibrium structures and vibrational frequencies discussed in this work were calculated using Gaussian 03 (Revision B.04, M. J. Frisch et al., Gaussian, Inc., Pittsburgh, PA, 2003), B3LYP, with a 6-311G(d,p) basis set.
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10
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33745121912
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note
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Convention identifies the N atom involved in the N-H bond in imidazole as atom 1, and the other heavy atoms in the ring labeled by counting in a clockwise direction in the case of the structure depicted in Fig. 1, i.e., C2, N3, etc.
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12
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33745125772
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note
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Vibronic coupling is an example of a breakdown of the Born-Oppenheimer separation, which applies when the vibrational and electronic degrees are coupled sufficiently strongly that they cannot be factored. In the case of an electric dipole forbidden transition, inclusion of a quantum of a nonsymmetric vibration changes the overall (vibronic) symmetry and permits the transition (with an intensity that depends on the degree of mixing of the vibrational and electronic wave functions).
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28
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33745177014
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note
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33.
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29
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33745169739
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note
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We are grateful to the Engineering and Physical Sciences Research Council UK for financial support via the Portfolio Partnership LASER and to K. N. Rosser for his outstanding practical support of this work.
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