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

Journal Article · · Journal of Chemical Theory and Computation
 [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)
+ Show Author Affiliations

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1478339
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 12 Vol. 11; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Relativistic time-dependent density functional theories journal January 2018
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