2016年5月
Computational Evidence of Inversion of L-1(a) and L-1(b)-Derived Excited States in Naphthalene Excimer Formation from ab Initio Multireference Theory with Large Active Space: DMRG-CASPT2 Study
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
- ,
- ,
- 巻
- 12
- 号
- 5
- 開始ページ
- 2366
- 終了ページ
- 2372
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1021/acs.jctc.6b00210
- 出版者・発行元
- AMER CHEMICAL SOC
The naphthalene molecule has two important lowest-lying singlet excited states, denoted L-1(a) and L-1(b). Association of the excited and ground state monomers yields a metastable excited dimer (excimer), which emits characteristic fluorescence. Here, we report a first computational result based on ab initio theory to corroborate that the naphthalene excimer fluorescence is L-1(a) parentage, resulting from inversion of L-1(a) and L-1(b)-derived dimer states. This inversion was hypothesized by earlier experimental studies; however, it has not been confirmed rigorously. In this study, the advanced multireference (MR) theory based on the density matrix renormalization group that enables using unprecedented large-size active space for describing significant electron correlation effects is used to provide accurate potential energy curves (PECs) of the excited states. The results evidenced the inversion of the PECs and accurately predicted transition energies for excimer fluorescence and monomer absorption. Traditional MR calculations with smaller active spaces and single-reference theory calculations exhibit serious inconsistencies with experimental observations.
- リンク情報
- ID情報
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- DOI : 10.1021/acs.jctc.6b00210
- ISSN : 1549-9618
- eISSN : 1549-9626
- Web of Science ID : WOS:000375810000024