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Title: Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations

Simulations of the n = 2 absorption spectra of HeN(N = 70, 150, 231, 300) clusters are reported, with nuclear configurations sampled by path integral molecular dynamics. The electronic structure is treated by a new approach, ALMO-CIS+CT, which is a formulation of configuration interaction singles (CIS) based on absolutely localized molecular orbitals (ALMOs). The method generalizes the previously reported ALMO-CIS model [K. D. Closser et al. J. Chem. Theory Comput. 11, 5791 (2015)] to include spatially localized charge transfer (CT) effects. It is designed to recover large numbers of excited states in atomic and molecular clusters, such as the entire n = 2 Rydberg band in helium clusters. ALMO-CIS+CT is shown to recover most of the error caused by neglecting charge transfer in ALMO-CIS and has comparable accuracy to standard CIS for helium clusters. For the n = 2 band, CT stabilizes states towards the blue edge by up to 0.5 eV. ALMO-CIS+CT retains the formal cubic scaling of ALMO-CIS with respect to system size. With improvements to the implementation over that originally reported for ALMO-CIS, ALMO-CIS+CT is able to treat helium clusters with hundreds of atoms using modest computing resources. Here, a detailed simulation of the absorption spectra associatedmore » with the 2s and 2p bands of helium clusters up to 300 atoms is reported, using path integral molecular dynamics with a spherical boundary condition to generate atomic configurations at 3 K. The main features of experimentally reported fluorescence excitation spectra for helium clusters are reproduced.« less
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Q-Chem Inc., Pleasanton, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 4; Related Information: © 2017 Author(s).; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1477256
Alternate Identifier(s):
OSTI ID: 1361725

Ge, Qinghui, Mao, Yuezhi, White, Alec F., Epifanovsky, Evgeny, Closser, Kristina D., and Head-Gordon, Martin. Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations. United States: N. p., Web. doi:10.1063/1.4973611.
Ge, Qinghui, Mao, Yuezhi, White, Alec F., Epifanovsky, Evgeny, Closser, Kristina D., & Head-Gordon, Martin. Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations. United States. doi:10.1063/1.4973611.
Ge, Qinghui, Mao, Yuezhi, White, Alec F., Epifanovsky, Evgeny, Closser, Kristina D., and Head-Gordon, Martin. 2017. "Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations". United States. doi:10.1063/1.4973611. https://www.osti.gov/servlets/purl/1477256.
@article{osti_1477256,
title = {Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations},
author = {Ge, Qinghui and Mao, Yuezhi and White, Alec F. and Epifanovsky, Evgeny and Closser, Kristina D. and Head-Gordon, Martin},
abstractNote = {Simulations of the n = 2 absorption spectra of HeN(N = 70, 150, 231, 300) clusters are reported, with nuclear configurations sampled by path integral molecular dynamics. The electronic structure is treated by a new approach, ALMO-CIS+CT, which is a formulation of configuration interaction singles (CIS) based on absolutely localized molecular orbitals (ALMOs). The method generalizes the previously reported ALMO-CIS model [K. D. Closser et al. J. Chem. Theory Comput. 11, 5791 (2015)] to include spatially localized charge transfer (CT) effects. It is designed to recover large numbers of excited states in atomic and molecular clusters, such as the entire n = 2 Rydberg band in helium clusters. ALMO-CIS+CT is shown to recover most of the error caused by neglecting charge transfer in ALMO-CIS and has comparable accuracy to standard CIS for helium clusters. For the n = 2 band, CT stabilizes states towards the blue edge by up to 0.5 eV. ALMO-CIS+CT retains the formal cubic scaling of ALMO-CIS with respect to system size. With improvements to the implementation over that originally reported for ALMO-CIS, ALMO-CIS+CT is able to treat helium clusters with hundreds of atoms using modest computing resources. Here, a detailed simulation of the absorption spectra associated with the 2s and 2p bands of helium clusters up to 300 atoms is reported, using path integral molecular dynamics with a spherical boundary condition to generate atomic configurations at 3 K. The main features of experimentally reported fluorescence excitation spectra for helium clusters are reproduced.},
doi = {10.1063/1.4973611},
journal = {Journal of Chemical Physics},
number = 4,
volume = 146,
place = {United States},
year = {2017},
month = {1}
}