(a) R2PI spectrum, (b) UVHB spectrum, and (c) UVD spectrum of DPM. Prominent peaks are labeled with their frequencies in wavenumbers from the origin
(a) Unsaturated and (b) saturated LIF spectra of DPM. Prominent peaks are labeled with their assignments and frequencies in wavenumbers from the origin.
High resolution UV spectra of the origin (lower trace) and the band (upper trace) of DPM.
SVLF spectra from (a) the origin and (b) the bands of DPM. Prominent peaks are labeled by their frequencies from the origin in wavenumbers. Scattered light at the excitation wavelength was subtracted out.
SVLF from (a) the origin, [(b)–(d)] the symmetric torsion progression, and (e) the band in DPM. Prominent peaks are labeled by their assignment. The stick spectra correspond to FC simulations using [(a)–(d)] and (e) . Scattered light at the excitation wavelength was subtracted out.
Cold (a) and warm (b) LIF spectra of the DPM origin region. The cold bands have been labeled in (a), while the prominent hot bands have been labeled in (b).
(a) SVLF spectrum, (b) SVLF spectrum, and (c) SVLF spectrum of DPM. FC predictions are shown in red as sticks beneath the experimental traces. The resonance peaks of (b) and (c) contain no information because scattered light from the experiment saturated the CCD detector and have been set to zero. The predicted stick intensity of the resonance peak in (b) has been divided by 16.
SVLF spectra of (a) the cold band, (b) the “saturated” band, (c) the “saturated” band, and (d) the hot band of DPM-. The unusual structure near the resonance frequency in (b)–(d) is due to saturation of the CCD by scattered light.
Close view of the clump emission in the SVLF of the origin ( band) in DPM. This spectrum was taken with higher laser power and slightly better resolution than the spectrum in Figs. 4 and 8 in order to better resolve the closely spaced set of transitions. Prominent peaks are labeled with their frequency from the excitation wavelength in wavenumbers and with their corresponding assignments of the ground-state levels involved.
Experimentally determined or extrapolated values for the energy levels of the and states of DPM-. The and symmetry levels have been separated for convenience. Each energy level is designated with a set of quantum numbers and a position (in wavenumbers) as shown in bottom right corner. The dotted lines indicate levels that are coupled.
Calculated relaxed potential energy curves of DPM at symmetry using TDDFT/B3LYP/. The lower curve (circles) is the ground-state potential. The excited state of symmetry, which is the state at the minimum-energy geometry of the ground state, is the upper solid curve (triangles). The upper dashed curve (squares) is the excited state of symmetry or the state at the geometry of the ground state. The markers represent the calculated points.
Major peaks in the DPM origin dispersed fluorescence spectrum.
Experimental frequencies of the lowest vibrational frequencies in , , and for both isotopomers of DPM.
Quantum number changes and contributions to the magnitude of the mixing coefficient between the origin and the indicated vibronic levels of DPM-.
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