Adiabatic potential energies of the , , , and electronic states of along the vibrational modes and . A sketch of the vibrational mode is also shown in the respective panel.
The PE spectrum of the coupled electronic states of . The experimental (reproduced from Ref. 18) and the present theoretical results are shown in the top and bottom panels, respectively. The intensity (in arbitrary units) is plotted along the energy (measured relative to electronic ground state of PA) of the final vibronic states. An energy offset of to the theoretical results is applied along the abscissa to reproduce the experimental adiabatic ionization energy of the band.
The MATI spectrum of the state. The experimental spectrum (reproduced from Ref. 15) is shown in the top panel. In the bottom panel, the coupled spectrum including vibrational modes and also the uncoupled state spectrum including the vibrational modes are shown (see text for details).
The time dependence of electronic (diabatic) populations of the (thin lines), (thick lines), (dashed lines), and (dotted lines) states of for an initial transition of the WP to the [panel (a)], [panel (b)], [panel (c)], and [panel (d)] in the coupled states dynamical treatment of discussed in Sec. IV A in the text.
The vibronic spectra of the coupled [panel (a)] and [panel (b)] electronic states of (see text for details). The vibrational energy level spectrum of the uncoupled state is shown as an insert in panel (a).
Schematic plots of the canonical MOs of benzene, fluorobenzene, and PA for the respective equilibrium configurations.
Details of the 36 vibrational modes and their frequencies (in ) of the ground electronic state of PA molecule. The theoretical numbers are harmonic, whereas the experimental ones are fundamentals. Wilson’s numbering of the vibrational modes is given in parentheses.
The linear coupling parameters for the , , and electronic states of the derived from the ab initio electronic structure data. The dimensionless coupling strengths, , are given in parentheses. The VIEs of the above electronic states are also given. All quantities are in eV.
The second-order coupling parameters (in eV) for the , , , and electronic states of the derived from the ab initio electronic structure data.
The linear interstate coupling parameters (in eV) of . The dimensionless coupling strengths, , are given in parentheses.
Normal mode combinations and sizes of the primitive and single-particle bases used in the MCTDH calculations for the coupled electronic states of .
Frequencies and coupling constants (in eV) of relevant vibrational modes for the JT active state of and their counterparts for the and electronic states of . The results for and are reproduced from Refs. 35 and 34, respectively.
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