TY - JOUR
T1 - Can TDDFT Describe Excited Electronic States of Naphthol Photoacids? A Closer Look with EOM-CCSD
AU - Acharya, Atanu
AU - Chaudhuri, Subhajyoti
AU - Batista, Victor S.
N1 - Funding Information:
*E-mail: atanu.acharya@yale.edu (A.A.). *E-mail: victor.batista@yale.edu (V.S.B.). ORCID Atanu Acharya: 0000-0002-6960-7789 Victor S. Batista: 0000-0002-3262-1237 Funding V.S.B. acknowledges support from NSF Grant CHE-1465108 and high-performance computing time from the National Energy Research Scientific Computing Center (NERSC) and the Yale High Performance Computing Center. A.A. acknowledges supercomputer time from the Extreme Science and Engineering Discovery Environment (XSEDE) under Grant TG-CHE170024. Notes The authors declare no competing financial interest.
Funding Information:
V.S.B. acknowledges support from NSF Grant CHE-1465108 and high-performance computing time from the National Energy Research Scientific Computing Center (NERSC) and the Yale High Performance Computing Center. A.A. acknowledges supercompter time from the Extreme Science and Engineering Discovery Environment (XSEDE) under Grant TG-CHE170024.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/2/13
Y1 - 2018/2/13
N2 - The 1Lb and 1La excited states of naphthols are characterized by using time-dependent density functional theory (TDDFT), configuration interaction with singles (CIS), and equation-of-motion coupled cluster singles and doubles (EOM-CCSD) methods. TDDFT fails dramatically at predicting the energy and ordering of the 1La and 1Lb excited states as observed experimentally, while EOM-CCSD accurately predicts the excited states as characterized by natural transition orbital analysis. The limitations of TDDFT are attributed to the absence of correlation from doubly excited configurations as well as the inconsistent description of excited electronic states of naphthol photoacids revealed by excitation analysis based on the one-electron transition density matrix.
AB - The 1Lb and 1La excited states of naphthols are characterized by using time-dependent density functional theory (TDDFT), configuration interaction with singles (CIS), and equation-of-motion coupled cluster singles and doubles (EOM-CCSD) methods. TDDFT fails dramatically at predicting the energy and ordering of the 1La and 1Lb excited states as observed experimentally, while EOM-CCSD accurately predicts the excited states as characterized by natural transition orbital analysis. The limitations of TDDFT are attributed to the absence of correlation from doubly excited configurations as well as the inconsistent description of excited electronic states of naphthol photoacids revealed by excitation analysis based on the one-electron transition density matrix.
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U2 - 10.1021/acs.jctc.7b01101
DO - 10.1021/acs.jctc.7b01101
M3 - Article
C2 - 29298059
AN - SCOPUS:85041963314
SN - 1549-9618
VL - 14
SP - 867
EP - 876
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 2
ER -