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Quadratic coupling treatment of the Jahn-Teller effect in the triply-degenerate electronic state of : Can one account for floppiness?
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10.1063/1.4768675
/content/aip/journal/jcp/137/21/10.1063/1.4768675
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/21/10.1063/1.4768675

Figures

Image of FIG. 1.
FIG. 1.

Adiabatic potential energies of the electronic state of along the dimensionless normal coordinate for the totally symmetric vibrational mode ν1. Energy of the ground electronic state of CH4 () at equilibrium configuration (Q = 0) is set to zero. The present vibronic model is shown by the solid line and the computed ab initio data by the solid dots.

Image of FIG. 2.
FIG. 2.

Same as in Fig. 1 along both the components (θ and ε) of e and ζ component of t 2 vibrational modes, respectively. See panels a–d.

Image of FIG. 3.
FIG. 3.

Same as in Fig. 1 along the simultaneous displacement of two coordinates of e and t 2 vibrational modes, respectively. See panels a–c.

Image of FIG. 4.
FIG. 4.

Same as in Fig. 1 along the simultaneous displacement of two coordinates of one component of e mode and one component of t 2 vibrational modes. See panels a–d.

Image of FIG. 5.
FIG. 5.

Vibronic band of the electronic state of . The intensity (in arbitrary units) is plotted along the energy (relative to minimum of the state of CH4) of the final vibronic states.

Image of FIG. 6.
FIG. 6.

Vibronic band of the electronic state of : (a) Spectrum reproduced from Ref. 31, (b) spectrum calculated by employing LVC Hamiltonian augmented by diagonal quadratic coupling parameter of totally symmetric ν1 vibration only, and (c) spectrum obtained from the present QVC Hamiltonian. The intensity is same as in Fig. 5.

Image of FIG. 7.
FIG. 7.

Vibrational energy levels of the electronic manifold of : (a) partial spectrum computed with the totally symmetric a 1 vibrational mode ν1, (b) partial spectrum computed with the JT active doubly degenerate e vibrational mode ν2, and (c) partial spectrum computed with two JT active triply degenerate t 2 vibrational modes ν3–ν4. The intensity (in arbitrary units) is plotted as a function of the energy of the final vibronic state. The zero of energy corresponds to the equilibrium of the electronic ground state CH4. The theoretical stick spectrum in each panel in convoluted with a Lorentzian function of 40 FWHM to generate the spectral envelope.

Image of FIG. 8.
FIG. 8.

Vibronic band of the electronic state of . The intensity is same as in Fig. 5. (a) Spectrum computed from the present QVC model Hamiltonian, (b) spectrum as in (a) but with readjustment of linear coupling parameters by −5% for ν2 mode and +5% for ν4 mode, (c) spectrum as in (a) but with readjustment of linear coupling parameters by −10% for ν2 mode and +10% for ν4 mode, and (d) spectrum as in (a) but with readjustment of linear coupling parameters by −10% for ν1 mode, −5% for ν2 mode, +10% for ν3 mode and +5% for ν4 mode, respectively.

Tables

Generic image for table
Table I.

Description of the vibrational modes of the electronic ground state of CH4 computed at the MP2/cc-pVTZ level of theory. While the theoretical frequencies are harmonic in nature the experimental ones are fundamentals. All values are in eV.

Generic image for table
Table II.

Coupling parameters in Eqs. (1)–(4) and (5a)–(5f) as obtained from CASSCF/MRCI calculations. The vertical ionization energy of the electronic state is also given. All values are in eV.

Generic image for table
Table III.

Normal mode combinations, sizes of both primitive and single-particle basis used in the WP propagation within the MCTDH framework in the coupled electronic manifold using the complete vibronic Hamiltonian of Eqs. (1)–(4) and (5a)–(5f). First column denotes the vibrational degrees of freedom (DOF) which are combined to particles. Second column gives the number of primitive basis functions for each DOF. Third column gives the number of single particle functions (SPFs) for each JT splitted electronic state.

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/content/aip/journal/jcp/137/21/10.1063/1.4768675
2012-12-07
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Quadratic coupling treatment of the Jahn-Teller effect in the triply-degenerate electronic state of CH4+: Can one account for floppiness?
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/21/10.1063/1.4768675
10.1063/1.4768675
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