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 S0-S1-S2 intersections (⁠gs∕ππ*∕nNπ* and gs∕ππ*∕nOπ*⁠) and an S1-S2-S3 intersection (⁠ππ*∕nNπ*∕nOπ*⁠). 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.

Topics
Ab-initio methods, Excitation energies, Complete-active space self-consistent field, Dynamical correlation, Potential energy surfaces, Multi-reference configuration interaction, Integral calculus, Radioactive decay, Quantum chemical dynamics, Geometric phases
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2008
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