Comparison of LC-TDDFT and ADC(2) Methods in Computations of Bright and Charge Transfer States in Stacked Oligothiophenes

Hao Li; Reed Nieman; Adélia J A Aquino; Hans Lischka; Sergei Tretiak

doi:10.1021/ct500072f

Comparison of LC-TDDFT and ADC(2) Methods in Computations of Bright and Charge Transfer States in Stacked Oligothiophenes

J Chem Theory Comput. 2014 Aug 12;10(8):3280-9. doi: 10.1021/ct500072f.

Authors

Hao Li¹, Reed Nieman², Adélia J A Aquino², Hans Lischka^{2

3}, Sergei Tretiak^{1

4}

Affiliations

¹ Theoretical Division, Center for Nonlinear Studies, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
² Department of Chemistry and Biochemistry, Texas Tech University , Lubbock, Texas 79409-1061, United States.
³ Institute for Theoretical Chemistry, University of Vienna , Währingerstrasse 17, A-1090, Vienna, Austria.
⁴ Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.

PMID: 26588297
DOI: 10.1021/ct500072f

Abstract

Long-range corrected time-dependent density functional theory (LC-TDDFT) has been applied to compute singlet vertical electronic excitations of oligothiophene molecules and their dimers and compared with the algebraic diagrammatic construction method to second order [ADC(2)], a wave function-based polarization propagator method. The excitation energies obtained from both methods agree to each other excellently. In particular, energetics of charge transfer states is concertedly reproduced. The linear response (LR) and the state specific (SS) approaches have been evaluated to appraise solvent effect on excited states. Benchmarked by the reference wave function method, the necessity of the SS treatment is justified in the prediction of charge transfer (CT) states under the TDDFT framework.