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Time-Dependent Linear-Response Variational Monte Carlo

Cornell Affiliated Author(s)

Author

Bastien Mussard
Emanuele Coccia
Roland Assaraf
Matthew Otten
Cyrus Umrigar
Julien Toulouse

Abstract

We present the extension of variational Monte Carlo (VMC) to the calculation of electronic excitation energies and oscillator strengths using time-dependent linear-response theory. By exploiting the analogy existing between the linear method for wave function optimization and the generalized eigenvalue equation of linear-response theory, we formulate the equations of linear-response VMC (LR-VMC). This LR-VMC approach involves the first- and second-order derivatives of the wave function with respect to the parameters. We perform first tests of the LR-VMC method within the Tamm–Dancoff approximation using single-determinant Jastrow–Slater wave functions with different Slater basis sets on some singlet and triplet excitations of the beryllium atom. Comparison with reference experimental data and with configuration-interaction-singles (CIS) results shows that LR-VMC generally outperforms CIS for excitation energies and is thus a promising approach for calculating electronic excited-state properties of atoms and molecules. © 2018 Elsevier Inc.

Date Published

Journal

Advances in Quantum Chemistry

Volume

76

Number of Pages

255-270,

URL

https://www.scopus.com/inward/record.uri?eid=2-s2.0-85022099074&doi=10.1016%2fbs.aiq.2017.05.005&partnerID=40&md5=dbeab798a1cc3442d8a87da202d01807

DOI

10.1016/bs.aiq.2017.05.005

Group (Lab)

Cyrus Umrigar Group

Funding Source

1534965

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