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Title: Superposition of Fragment Excitations for Excited States of Large Clusters with Application to Helium Clusters

Abstract

We develop a local excited-state method, based on the configuration interaction singles (CIS) wave function, for large atomic and molecular clusters. This method exploits the properties of absolutely localized molecular orbitals (ALMOs), which strictly limits the total number of excitations, and results in formal scaling with the third power of the system size for computing the full spectrum of ALMO-CIS excited states. Here, the derivation of the equations and design of the algorithm are discussed in detail, with particular emphasis on the computational scaling. Clusters containing ~500 atoms were used in evaluating the scaling, which agrees with the theoretical predictions, and the accuracy of the method is evaluated with respect to standard CIS. Finally, a pioneering application to the size dependence of the helium cluster spectrum is also presented for clusters of 25-231 atoms, the largest of which results in the computation of 2310 excited states per sampled cluster geometry.

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry, Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry, Dept. of Chemistry
  3. Q-Chem, Inc., Pleasanton, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1478339
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 11; Journal Issue: 12; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING

Citation Formats

Closser, Kristina D., Ge, Qinghui, Mao, Yuezhi, Shao, Yihan, and Head-Gordon, Martin. Superposition of Fragment Excitations for Excited States of Large Clusters with Application to Helium Clusters. United States: N. p., 2015. Web. doi:10.1021/acs.jctc.5b00703.
Closser, Kristina D., Ge, Qinghui, Mao, Yuezhi, Shao, Yihan, & Head-Gordon, Martin. Superposition of Fragment Excitations for Excited States of Large Clusters with Application to Helium Clusters. United States. doi:10.1021/acs.jctc.5b00703.
Closser, Kristina D., Ge, Qinghui, Mao, Yuezhi, Shao, Yihan, and Head-Gordon, Martin. Fri . "Superposition of Fragment Excitations for Excited States of Large Clusters with Application to Helium Clusters". United States. doi:10.1021/acs.jctc.5b00703. https://www.osti.gov/servlets/purl/1478339.
@article{osti_1478339,
title = {Superposition of Fragment Excitations for Excited States of Large Clusters with Application to Helium Clusters},
author = {Closser, Kristina D. and Ge, Qinghui and Mao, Yuezhi and Shao, Yihan and Head-Gordon, Martin},
abstractNote = {We develop a local excited-state method, based on the configuration interaction singles (CIS) wave function, for large atomic and molecular clusters. This method exploits the properties of absolutely localized molecular orbitals (ALMOs), which strictly limits the total number of excitations, and results in formal scaling with the third power of the system size for computing the full spectrum of ALMO-CIS excited states. Here, the derivation of the equations and design of the algorithm are discussed in detail, with particular emphasis on the computational scaling. Clusters containing ~500 atoms were used in evaluating the scaling, which agrees with the theoretical predictions, and the accuracy of the method is evaluated with respect to standard CIS. Finally, a pioneering application to the size dependence of the helium cluster spectrum is also presented for clusters of 25-231 atoms, the largest of which results in the computation of 2310 excited states per sampled cluster geometry.},
doi = {10.1021/acs.jctc.5b00703},
journal = {Journal of Chemical Theory and Computation},
number = 12,
volume = 11,
place = {United States},
year = {2015},
month = {11}
}

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