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

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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 1A1 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.
Original languageEnglish
Article number154103
Number of pages11
JournalJournal of Chemical Physics
Volume139
Issue number15
DOIs
Publication statusPublished - 21 Oct 2013

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