An accurate theoretical prediction of the vibrational spectra for a pure nitrogen ring (cyclic- molecule is obtained up to the energy of the conical intersection. A coupled-channel approach using the hyperspherical coordinates and the recently published ab initio potential energy surface [D. Babikov, P. Zhang, and K. Morokuma, J. Chem. Phys. 121, 6743 (2004)] is employed. Two independent sets of calculations are reported: In the first set, the standard Born–Oppenheimer approximation is used and the geometric phase effects are totally neglected. In the second set, the generalized Born–Oppenhimer approximation is used and the geometric phase effects due to the conical intersection are accurately treated. All vibrational states are analyzed and assigned in terms of the normal vibration mode quantum numbers. The magnitude of the geometric phase effect is determined for each state. One important finding is an unusually large magnitude of the geometric phase effects in the cyclic- it is ∼100 cm−1 for the low-lying vibrational states and exceeds 600 cm−1 for several upper states. On average, this is almost two orders of magnitude larger than in the previously reported studies. This unique example suggests a favorable path to experimental validation.
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22 January 2005
Research Article|
January 11 2005
Cyclic- II. Significant geometric phase effects in the vibrational spectra
Dmitri Babikov;
Dmitri Babikov
Chemistry Department, Marquette University, Wehr Chemistry Building, Milwaukee, Wisconsin 53201
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Brian K. Kendrick;
Brian K. Kendrick
Theoretical Chemistry and Molecular Physics (T-12), Los Alamos National Laboratory, Los Alamos MS B268, New Mexico 87545
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Peng Zhang;
Peng Zhang
Department of Chemistry, Emory University, Chemistry Building, Atlanta, Georgia 30322
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Keiji Morokuma
Keiji Morokuma
Department of Chemistry, Emory University, Chemistry Building, Atlanta, Georgia 30322
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Dmitri Babikov
Brian K. Kendrick
Peng Zhang
Keiji Morokuma
Chemistry Department, Marquette University, Wehr Chemistry Building, Milwaukee, Wisconsin 53201
J. Chem. Phys. 122, 044315 (2005)
Article history
Received:
July 30 2004
Accepted:
October 05 2004
Citation
Dmitri Babikov, Brian K. Kendrick, Peng Zhang, Keiji Morokuma; Cyclic- II. Significant geometric phase effects in the vibrational spectra. J. Chem. Phys. 22 January 2005; 122 (4): 044315. https://doi.org/10.1063/1.1824905
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