Can TDDFT Describe Excited Electronic States of Naphthol Photoacids? A Closer Look with EOM-CCSD

Atanu Acharya; Subhajyoti Chaudhuri; Victor S. Batista

doi:10.1021/acs.jctc.7b01101

Can TDDFT Describe Excited Electronic States of Naphthol Photoacids? A Closer Look with EOM-CCSD

Atanu Acharya, Subhajyoti Chaudhuri, Victor S. Batista

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

The ¹L_b and ¹L_a 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 ¹L_a and ¹L_b 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.

Original language	English (US)
Pages (from-to)	867-876
Number of pages	10
Journal	Journal of Chemical Theory and Computation
Volume	14
Issue number	2
DOIs	https://doi.org/10.1021/acs.jctc.7b01101
State	Published - Feb 13 2018
Externally published	Yes

ASJC Scopus subject areas

Computer Science Applications
Physical and Theoretical Chemistry

Access to Document

10.1021/acs.jctc.7b01101

Cite this

@article{99d01acd11a44aeca0db8e1ee222dcab,

title = "Can TDDFT Describe Excited Electronic States of Naphthol Photoacids? A Closer Look with EOM-CCSD",

abstract = "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.",

author = "Atanu Acharya and Subhajyoti Chaudhuri and Batista, {Victor S.}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = feb,

day = "13",

doi = "10.1021/acs.jctc.7b01101",

language = "English (US)",

volume = "14",

pages = "867--876",

journal = "Journal of Chemical Theory and Computation",

issn = "1549-9618",

publisher = "American Chemical Society",

number = "2",

}

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.

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.

UR - http://www.scopus.com/inward/record.url?scp=85041963314&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85041963314&partnerID=8YFLogxK

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 -

Can TDDFT Describe Excited Electronic States of Naphthol Photoacids? A Closer Look with EOM-CCSD

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this