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Title: Localized diabatization applied to excitons in molecular crystals

Abstract

Traditional ab initio electronic structure calculations of periodic systems yield delocalized eigenstates that should be understood as adiabatic states. For example, excitons are bands of extended states which superimpose localized excitations on every lattice site. However, in general, in order to study the effects of nuclear motion on exciton transport, it is standard to work with a localized description of excitons, especially in a hopping regime; even in a band regime, a localized description can be helpful. To extract localized excitons from a band requires essentially a diabatization procedure. In this paper, three distinct methods are proposed for such localized diabatization: (i) a simple projection method, (ii) a more general Pipek-Mezey localization scheme, and (iii) a variant of Boys diabatization. Approaches (i) and (ii) require localized, single-particle Wannier orbitals, while approach (iii) has no such dependence. Lastly, these methods should be very useful for studying energy transfer through solids with ab initio calculations.

Authors:
ORCiD logo [1];  [2]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1373202
Grant/Contract Number:  
AC02-76SF00515; FA9950-13-1-0157
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS

Citation Formats

Jin, Zuxin, and Subotnik, Joseph E. Localized diabatization applied to excitons in molecular crystals. United States: N. p., 2017. Web. doi:10.1063/1.4986952.
Jin, Zuxin, & Subotnik, Joseph E. Localized diabatization applied to excitons in molecular crystals. United States. doi:10.1063/1.4986952.
Jin, Zuxin, and Subotnik, Joseph E. Wed . "Localized diabatization applied to excitons in molecular crystals". United States. doi:10.1063/1.4986952. https://www.osti.gov/servlets/purl/1373202.
@article{osti_1373202,
title = {Localized diabatization applied to excitons in molecular crystals},
author = {Jin, Zuxin and Subotnik, Joseph E.},
abstractNote = {Traditional ab initio electronic structure calculations of periodic systems yield delocalized eigenstates that should be understood as adiabatic states. For example, excitons are bands of extended states which superimpose localized excitations on every lattice site. However, in general, in order to study the effects of nuclear motion on exciton transport, it is standard to work with a localized description of excitons, especially in a hopping regime; even in a band regime, a localized description can be helpful. To extract localized excitons from a band requires essentially a diabatization procedure. In this paper, three distinct methods are proposed for such localized diabatization: (i) a simple projection method, (ii) a more general Pipek-Mezey localization scheme, and (iii) a variant of Boys diabatization. Approaches (i) and (ii) require localized, single-particle Wannier orbitals, while approach (iii) has no such dependence. Lastly, these methods should be very useful for studying energy transfer through solids with ab initio calculations.},
doi = {10.1063/1.4986952},
journal = {Journal of Chemical Physics},
number = 24,
volume = 146,
place = {United States},
year = {2017},
month = {6}
}

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