The geometry of 1-propynyl.
Analysis of the accuracy of fits. Log plots of the magnitude of the predicted value of parameter vs ab initio value. Points used are found in sets and (circles) and (triangles). The left and right columns correspond to and determined data, respectively, while panels [(a) and (d)], [(b) and (e)], and [(c) and (f)] are energies, energy gradients, and coupling gradients, respectively.
Schematic depiction of the critical points on the 1-propynyl surface.
Comparison of adiabatic spectrum of 1-propynide- (a) and 1-propynide- (b) to the PE and SEVI experiments (see text). The state peaks surround dark (blue on-line) lines, the peaks surround grey (green on-line) lines, and the composite spectra envelope is a solid black line. The SEVI and PE spectra are dashed and dotted (red on-line) lines, respectively. The simulated spectrum was obtained employing a Gaussian convolution with the full width at half maximum (FWHM) of .
Determination of relative transition dipole moments. (a) Comparison of PE spectrum (dotted) with the spectrum (solid) in which transition dipole moments are equal: . Panel (b) presents simulated spectra for which (dotted) and 0 (solid). Panel (c) presents the simulated spectrum with the optimal choice of (solid) with the PE experimental spectrum (dotted). All simulated spectra employ a Gaussian convolution for which .
Comparison of the 1-propynide- SEVI (a) (dashed) and PE (b) (dotted) spectra with the best simulated spectrum (solid). The simulated spectra in (a) and (b) employ and , respectively. The peaks are labeled according to Zhou et al. (Ref. 27).
Comparison of the 1-propynide- SEVI spectrum (dashed) with the best simulated spectrum (solid). The simulated spectrum display peaks for which . The peaks are labeled according to Zhou et al. (Ref. 27).
Geometric parameters of key stationary points (bond lengths in Å and angles in deg). Columns 4–6 refer to , and columns 7–9 refer to .
ab initio and determined energies .
ab initio and predicted harmonic frequencies . Columns 4–6 (7–9) refer to the state of 1-propynyl- (1-propynyl-).
for converged vibronic basis sets.
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