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Jahn-Teller effect in and : Conformational isomerism, tunneling-rotation structure, and the location of conical intersections
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10.1063/1.2716394
/content/aip/journal/jcp/126/15/10.1063/1.2716394
http://aip.metastore.ingenta.com/content/aip/journal/jcp/126/15/10.1063/1.2716394

Figures

Image of FIG. 1.
FIG. 1.

Schematic representation of several stationary points on the potential energy surface of and their topological relationships. The empty circles correspond to the three equivalent minima of the more stable isomer . The squares represent the three equivalent minima of the isomer . The filled circles on four faces of the octahedron represent the structures possessing a doubly degenerate ground electronic state and the center of the remaining four faces correspond to the structures with a nondegenerate ground state. The structure of the and stationary points that are of importance in the present study are depicted.

Image of FIG. 2.
FIG. 2.

Tunneling levels of with zero total angular momentum and ground vibronic state of (full lines). The quantities and represent the tunneling integrals for the isomers and , respectively, ZPED stands for the zero-point energy difference between these isomers, and IE is the adiabatic ionization energy. describes the zero-point energy difference in the absence of tunneling.

Image of FIG. 3.
FIG. 3.

Tunneling levels of with zero total angular momentum and ground vibronic state of (full lines). The quantities and represent the tunneling integrals for the isomers and , respectively, ZPED stands for the zero-point energy difference between these isomers, and IE is the adiabatic ionization energy. describes the zero-point energy difference in the absence of tunneling.

Image of FIG. 4.
FIG. 4.

Axis systems used in the derivation of the rotational Hamiltonian. The principal axis system of the neutral molecule is depicted on the left-hand side (a). After distortion of the molecule to the equilibrium structure of the cation (b), the axis system is translated to the new center of mass and then rotated about the axis until it coincides with the principal axis system of the distorted molecule (c).

Image of FIG. 5.
FIG. 5.

Correlation diagram of the eigenvalues of the tunneling-rotation Hamiltonian (14) as a function of the tunneling integral for [panel (a)] and [panel (b)]. In the limit , all levels are threefold degenerate and coincide with the pattern of an asymmetric top which is depicted on the left-hand side. The full lines correspond to levels of rovibronic symmetry or in the group, whereas the dashed lines correspond to levels of symmetry . The vibronic symmetries of the tunneling sublevels are indicated on the right-hand side of the figure by large capital letters.

Image of FIG. 6.
FIG. 6.

PFI-ZEKE photoelectron spectrum (full line) and photoionization spectrum (dashed line) of . The PFI-ZEKE photoelectron spectrum was recorded using a sequence of pulsed electric fields of and . The position of the zero-point-corrected ab initio barrier for isomerization is indicated by an arrow.

Image of FIG. 7.
FIG. 7.

Lowest band in the PFI-ZEKE photoelectron spectrum of corresponding to isomer [trace (a)] and simulation [trace (b)]. The PFI-ZEKE photoelectron spectrum was recorded using a sequence of pulsed electric fields of and . Trace (b) shows a theoretical stick spectrum consisting of transitions to levels of rovibronic symmetry or (full sticks) and transitions to levels of rovibronic symmetry (dotted sticks). The stick spectrum has been convoluted with a Gaussian line shape of FWHM.

Image of FIG. 8.
FIG. 8.

Second lowest band in the PFI-ZEKE photoelectron spectrum of corresponding to isomer [trace (a)] and simulation [trace (b)]. The PFI-ZEKE photoelectron spectrum was recorded using a sequence of pulsed electric fields of and . Trace (b) shows a theoretical stick spectrum consisting of transitions to levels of rovibronic symmetry or (full sticks) and transitions to levels of rovibronic symmetry (dotted sticks). The stick spectrum has been convoluted with a Gaussian line shape of FWHM.

Image of FIG. 9.
FIG. 9.

PFI-ZEKE photoelectron spectrum (full line) and photoionization spectrum (dashed line) of . The PFI-ZEKE photoelectron spectrum was recorded using a sequence of pulsed electric fields of and . The position of the zero-point-corrected ab initio barrier for isomerization is indicated by an arrow.

Image of FIG. 10.
FIG. 10.

Lowest band in the PFI-ZEKE photoelectron spectrum of corresponding to isomer [trace (a)] and simulation [trace (b)]. The PFI-ZEKE photoelectron spectrum was recorded using a sequence of pulsed electric fields of and . Trace (b) shows a theoretical stick spectrum consisting of transitions to levels of rovibronic symmetry or (full sticks) and transitions to levels of rovibronic symmetry (dotted sticks). The stick spectrum has been convoluted with a Gaussian line shape of FWHM.

Image of FIG. 11.
FIG. 11.

Second lowest band in the PFI-ZEKE photoelectron spectrum of corresponding to isomer [trace (a)] and simulation [trace (b)]. The PFI-ZEKE photoelectron spectrum was recorded using a sequence of pulsed electric fields of and . Trace (b) shows a theoretical stick spectrum consisting of transitions to levels of rovibronic symmetry or (full sticks) and transitions to levels of rovibronic symmetry (dotted sticks). The stick spectrum has been convoluted with a Gaussian line shape of FWHM.

Tables

Generic image for table
Table I.

Reverse correlation table of irreducible representations of the point group to the molecular symmetry group.

Generic image for table
Table II.

Constants calculated using the experimental structure of determined in Ref. 19 and adjusted to reproduce the experimental spectra. , , are the asymmetric top rotational constants, is the angle by which the axis has been tilted away from the symmetric top principal axis in the rotation of the axis system, is the tunneling splitting, IE is the adiabatic ionization energy of the more stable isomer, and ZPED is the zero-point energy difference between the two isomers.

Generic image for table
Table III.

Measured line positions and deviations from the calculated line positions of the origin band of the photoionizing transition of . , , and represent the vibronic and the rovibronic symmetries in the molecular symmetry group for the neutral and the ionic states, respectively.

Generic image for table
Table IV.

Measured line positions and deviations from the calculated line positions of the origin band of the photoionizing transition of . , , and represent the vibronic and the rovibronic symmetries in the molecular symmetry group for the neutral and the ionic states, respectively.

Generic image for table
Table V.

Barrier heights at the CCSD(T)/cc-pVTZ level of ab initio theory after harmonic zero-point corrections. The barrier heights for pseudorotations exchanging identical nuclei are given with respect to the minima of the corresponding isomers, whereas the isomerization barriers are given with respect to the minimum of the more stable isomer. The purely electronic barrier height amounts to (Ref. 21).

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/content/aip/journal/jcp/126/15/10.1063/1.2716394
2007-04-16
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Jahn-Teller effect in CH3D+ and CD3H+: Conformational isomerism, tunneling-rotation structure, and the location of conical intersections
http://aip.metastore.ingenta.com/content/aip/journal/jcp/126/15/10.1063/1.2716394
10.1063/1.2716394
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