Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo

We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently introduced variation-after-response method [E. Neuscamman, J. Chem. Phys. 145, 081103 (2016)], this ansatz allows a crucial orbital...

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Bibliographic Details
Published in:The Journal of chemical physics 2017-11, Vol.147 (19), p.194101-194101
Main Authors: Blunt, N. S., Neuscamman, Eric
Format: Article
Language:English
Subjects:
ATOMIC AND MOLECULAR PHYSICS
Charge transfer
Configuration interaction
Configuration management
Electron correlation
Electronic structure theory
Excited states
Lithium fluoride
Monte Carlo simulation
Quantum Monte Carlo
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Summary:We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently introduced variation-after-response method [E. Neuscamman, J. Chem. Phys. 145, 081103 (2016)], this ansatz allows a crucial orbital optimization step to be performed beyond a configuration interaction singles expansion, while only requiring calculation of two Slater determinant objects. We demonstrate this ansatz for the illustrative example of the stretched LiF molecule, for a range of excited states of formaldehyde, and finally for the more challenging ethylene-tetrafluoroethylene molecule.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4998197