Pyrazine excited states revisited using the extended multi-state complete active space second-order perturbation method

Abstract

We demonstrate that the recently developed extended multi-state complete active space second-order perturbation theory (XMS-CASPT2) [Shiozaki et al., J. Chem. Phys., 2011, 135, 081106] provides qualitatively correct potential energy surfaces for low-lying excited singlet states of pyrazine, while the potential energy surfaces of the standard MS-CASPT2 methods are ill-behaved near the crossing point of two reference potential energy surfaces. The XMS-CASPT2 method is based on the extended multi-configuration quasi-degenerate perturbation theory proposed earlier by Granovsky [J. Chem. Phys., 2011, 134, 214113]. We show that the conical intersection at the XMS-CASPT2 level can be described without artifacts if the entire method is invariant with respect to any unitary rotations of the reference functions. The photoabsorption spectra of the 1¹B_3u and 1¹B_2u states of pyrazine are simulated, based on a vibronic-coupling model Hamiltonian. The XMS-CASPT2 spectrum of the 1¹B_3u band is found to be comparable to the one computed by a more expensive multireference configuration interaction (MRCI) method, while the XMS-CASPT2 simulation of the 1¹B_2u band is slightly inferior to the MRCI one.