Excited states in variational Monte Carlo using a penalty method.

In this article, the authors present a technique using variational Monte Carlo to solve for excited states of electronic systems. This technique is based on enforcing orthogonality to lower energy states, which results in a simple variational principle for the excited states. Energy optimization is then used to solve for the excited states. This technique is applied to the well-characterized benzene molecule, in which ∼10 000 parameters are optimized for the first 12 excited states. Agreement within ∼0.2 eV is obtained with higher scaling coupled cluster methods; small disagreements with experiment are likely due to vibrational effects.