Theoretical investigation of the ground and excited states of coumarin 151 and coumarin 120

Robert J. Cave, Kieron Burke, Ed Castner

Research output: Contribution to journalArticle

139 Citations (Scopus)

Abstract

We present calculations of various properties of the ground and excited states of Coumarins 151 and 120. These and related coumarins are important in investigating ultrafast solvation processes in liquids and complex solutions as well as being important acceptors in model electron-transfer systems. We calculate the following: (1) the electronic excitation energies to several low-lying singlet states, (2) ground and excited-state dipole moments, (3) solvation effects on excitation energies, and (4) the properties of single Coumarin 151-water complexes. We test our Time-Dependent Density Functional Theory (TDDFT) calculations against CASSCF, CASPT2 (both single and multistate versions), CIS, and ZINDO. Using TDDFT, we find excellent agreement with experimental S1 ← S0 excitation energies. On the basis of these results, we address several outstanding questions for these systems and find: (1) that TICT-formation is unlikely upon photexcitation for gas-phase C151, (2) a greater tendency toward a planar amine group for the S1 state than for the ground state, (3) significant differences between our gas-phase ground-state dipole moment and the experimental value, and (4) TDDFT results for water-Coumarin 151 complexes are in good agreement with the experimental results of Topp and co-workers.

Original languageEnglish
Pages (from-to)9294-9305
Number of pages12
JournalJournal of Physical Chemistry A
Volume106
Issue number40
DOIs
Publication statusPublished - Oct 10 2002

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Excited states
Ground state
Excitation energy
Density functional theory
ground state
Solvation
Dipole moment
excitation
density functional theory
Gases
solvation
Coumarins
dipole moments
Water
vapor phases
Commonwealth of Independent States
Amines
water
energy
amines

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical investigation of the ground and excited states of coumarin 151 and coumarin 120. / Cave, Robert J.; Burke, Kieron; Castner, Ed.

In: Journal of Physical Chemistry A, Vol. 106, No. 40, 10.10.2002, p. 9294-9305.

Research output: Contribution to journalArticle

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