TY - JOUR
T1 - Time propagation of electronic wavefunctions using nonorthogonal determinant expansions
AU - Dong, Xinju
AU - Thompson, Lee M.
N1 - Publisher Copyright:
© 2024 Author(s).
PY - 2024/1/14
Y1 - 2024/1/14
N2 - The use of truncated configuration interaction in real-time time-dependent simulations of electron dynamics provides a balance of computational cost and accuracy, while avoiding some of the failures associated with real-time time-dependent density functional theory. However, low-order truncated configuration interaction also has limitations, such as overestimation of polarizability in configuration interaction singles, even when perturbative doubles are included. Increasing the size of the determinant expansion may not be computationally feasible, and so, in this work, we investigate the use of nonorthogonality in the determinant expansion to establish the extent to which higher-order substitutions can be recovered, providing an improved description of electron dynamics. Model systems are investigated to quantify the extent to which different methods accurately reproduce the (hyper)polarizability, including the high-harmonic generation spectrum of H2, water, and butadiene.
AB - The use of truncated configuration interaction in real-time time-dependent simulations of electron dynamics provides a balance of computational cost and accuracy, while avoiding some of the failures associated with real-time time-dependent density functional theory. However, low-order truncated configuration interaction also has limitations, such as overestimation of polarizability in configuration interaction singles, even when perturbative doubles are included. Increasing the size of the determinant expansion may not be computationally feasible, and so, in this work, we investigate the use of nonorthogonality in the determinant expansion to establish the extent to which higher-order substitutions can be recovered, providing an improved description of electron dynamics. Model systems are investigated to quantify the extent to which different methods accurately reproduce the (hyper)polarizability, including the high-harmonic generation spectrum of H2, water, and butadiene.
UR - http://www.scopus.com/inward/record.url?scp=85181999367&partnerID=8YFLogxK
U2 - 10.1063/5.0179601
DO - 10.1063/5.0179601
M3 - Article
C2 - 38189613
AN - SCOPUS:85181999367
SN - 0021-9606
VL - 160
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 2
M1 - 024106
ER -