Three-state conical intersections have been located and characterized for cytosine and its analog 5-methyl-2-pyrimidinone using multireference configuration-interaction ab initio methods. The potential energy surfaces for each base contain three different three-state intersections: two different intersections ( and ) and an intersection (). Two-state seam paths from these intersections are shown to be connected to previously reported two-state conical intersections. Nonadiabatic coupling terms have been calculated, and the effects of the proximal third state on these quantities are detailed. In particular, it is shown that when one of these loops incorporates more than one seam point, there is a profound and predictable effect on the phase of the nonadiabatic coupling terms, and as such provides a diagnostic for the presence and location of additional seams. In addition, it is shown that each of the three three-state conical intersections located on cytosine and 5-methyl-2-pyrimidinone is qualitatively similar between the two bases in terms of energies and character, implying that, like with the stationary points and two-state conical intersections previously reported for these two bases, there is an underlying pattern of energy surfaces for 2-pyrimidinone bases, in general, and this pattern also includes three-state conical intersections.
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7 June 2008
Research Article|
June 05 2008
Three-state conical intersections in cytosine and pyrimidinone bases Available to Purchase
Kurt A. Kistler;
Kurt A. Kistler
Department of Chemistry,
Temple University
, Philadelphia, Pennsylvania 19122, USA
Search for other works by this author on:
Spiridoula Matsika
Spiridoula Matsika
a)
Department of Chemistry,
Temple University
, Philadelphia, Pennsylvania 19122, USA
Search for other works by this author on:
Kurt A. Kistler
Department of Chemistry,
Temple University
, Philadelphia, Pennsylvania 19122, USA
Spiridoula Matsika
a)
Department of Chemistry,
Temple University
, Philadelphia, Pennsylvania 19122, USA
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected].
J. Chem. Phys. 128, 215102 (2008)
Article history
Received:
April 07 2008
Accepted:
April 29 2008
Citation
Kurt A. Kistler, Spiridoula Matsika; Three-state conical intersections in cytosine and pyrimidinone bases. J. Chem. Phys. 7 June 2008; 128 (21): 215102. https://doi.org/10.1063/1.2932102
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