Gas-Phase Infrared and NMR Investigation of the Conformers of Diacetone Diperoxide (DADP)

Chunlei Guo, John Persons, Jeffrey N. Woodford, Gerard S. Harbison

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Gas-phase infrared measurements of diacetone diperoxide (DADP) indicate a chair conformation with less than 5% of the predicted twist conformer. Vibrational frequencies are very similar to those previously measured in the solid state. Solution NMR measurements using 2D exchange spectroscopy (EXSY) also set a very low maximum limit on the equilibrium population of the twist conformer, with a room-temperature free-energy difference in excess of 14.5 kJ/mol. These experimental results are in accord with high-level quantum calculations incorporating full thermochemistry and solvation effects, which indicate a free-energy difference in the range of 14.7-17.5 kJ/mol in polar solvents.

Original languageEnglish (US)
Pages (from-to)10221-10228
Number of pages8
JournalJournal of Physical Chemistry A
Volume119
Issue number40
DOIs
StatePublished - Oct 8 2015

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Free energy
Gases
free energy
Nuclear magnetic resonance
vapor phases
Thermochemistry
Infrared radiation
nuclear magnetic resonance
thermochemistry
Solvation
Vibrational spectra
seats
solvation
Conformations
Ion exchange
Spectroscopy
solid state
room temperature
spectroscopy
Temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Gas-Phase Infrared and NMR Investigation of the Conformers of Diacetone Diperoxide (DADP). / Guo, Chunlei; Persons, John; Woodford, Jeffrey N.; Harbison, Gerard S.

In: Journal of Physical Chemistry A, Vol. 119, No. 40, 08.10.2015, p. 10221-10228.

Research output: Contribution to journalArticle

Guo, Chunlei ; Persons, John ; Woodford, Jeffrey N. ; Harbison, Gerard S. / Gas-Phase Infrared and NMR Investigation of the Conformers of Diacetone Diperoxide (DADP). In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 40. pp. 10221-10228.
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