State-averaged Monte Carlo configuration interaction applied to electronically excited states

Abstract

We introduce state-averaging into the method of Monte Carlo configuration interaction (SA-MCCI) to allow the stable and efficient calculation of excited states. We show that excited potential curves for H3, including a crossing with the ground state, can be accurately reproduced using a small fraction of the full configuration interaction (FCI) space. A recently introduced error measure for potential curves [J. P. Coe and M. J. Paterson, J. Chem. Phys. 137, 204108 (2012)] is also shown to be a fair approach when considering potential curves for multiple states. We demonstrate that potential curves for LiF using SA-MCCI agree well with the FCI results and the avoided crossing occurs correctly. The seam of conical intersections for CH2 found by Yarkony [J. Chem. Phys. 104, 2932 (1996)] is used as a test for SA-MCCI and we compare potential curves from SA-MCCI with FCI results for this system for the first three triplet states. We then demonstrate the improvement from using SA-MCCI on the dipole of the 2 (1)A1 state of carbon monoxide. We then look at vertical excitations for small organic molecules up to the size of butadiene where the SA-MCCI energies and oscillator strengths are compared with CASPT2 values [M. Schreiber, M. R. Silva-Junior, S. P. A. Sauer, and W. Thiel, J. Chem. Phys. 128, 134110 (2008)]. We finally see if the SA-MCCI results for these excitation energies can be improved by using MCCIPT2 with approximate natural orbitals when the PT2 space is not onerously large.