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Excited states using semistochastic heat-bath configuration interaction

Cornell Affiliated Author(s)

Author

Adam Holmes
C. Umrigar
Sandeep Sharma

Abstract

We extend our recently developed heat-bath configuration interaction (HCI) algorithm, and our semistochastic algorithm for performing multireference perturbation theory, to calculate excited-state wavefunctions and energies. We employ time-reversal symmetry, which reduces the memory requirements by more than a factor of two. An extrapolation technique is introduced to reliably extrapolate HCI energies to the full CI limit. The resulting algorithm is used to compute fourteen low-lying potential energy surfaces of the carbon dimer using the cc-pV5Z basis set, with an estimated error in energy of 30-50 μHa compared to full CI. The excitation energies obtained using our algorithm have a mean absolute deviation of 0.02 eV compared to experimental values. © 2017 Author(s).

Date Published

Journal

Journal of Chemical Physics

Volume

147

Issue

16

URL

https://www.scopus.com/inward/record.uri?eid=2-s2.0-85032588457&doi=10.1063%2f1.4998614&partnerID=40&md5=d4e79eb74cac1c5466189870cf89748c

DOI

10.1063/1.4998614

Group (Lab)

Cyrus Umrigar Group

Funding Source

1534965

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