Auto-oligomerization and hydration of pyrrole revealed by x-ray absorption spectroscopy

Journal Article · Mon Sep 21 00:00:00 EDT 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3223539· OSTI ID:21559773

Schwartz, Craig P; Uejio, Janel S; Duffin, Andrew M; England, Alice H; Saykally, Richard J ^[1]; Prendergast, David ^[2]

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1. Department of Chemistry, University of California, Berkeley, California 94720-1460 (United States) and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
2. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

Near edge x-ray absorption fine structure spectra have been measured at the carbon and nitrogen K-edges of the prototypical aromatic molecule, pyrrole, both in the gas phase and when solvated in water, and compared with spectra simulated using a combination of classical molecular dynamics and first principles density functional theory in the excited state core hole approximation. The excellent agreement enabled detailed assignments. Pyrrole is highly reactive, particularly in water, and reaction products formed by the auto-oligomerization of pyrrole are identified. The solvated spectra have been measured at two different temperatures, indicating that the final states remain largely unaffected by both hydration and temperature. This is somewhat unexpected, since the nitrogen in pyrrole can donate a hydrogen bond to water.

• OSTI ID: 21559773
• Journal Information: Journal of Chemical Physics, Vol. 131, Issue 11; Other Information: DOI: 10.1063/1.3223539; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION
ABSORPTION SPECTROSCOPY
ALLOCATIONS
APPROXIMATIONS
CARBON
DENSITY FUNCTIONAL METHOD
EXCITED STATES
FINE STRUCTURE
HYDRATION
HYDROGEN
MOLECULAR DYNAMICS METHOD
NITROGEN
PYRROLES
SIMULATION
SPECTRA
WATER
X RADIATION
X-RAY SPECTROSCOPY
AZOLES
CALCULATION METHODS
ELECTROMAGNETIC RADIATION
ELEMENTS
ENERGY LEVELS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
IONIZING RADIATIONS
NONMETALS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
RADIATIONS
SOLVATION
SORPTION
SPECTROSCOPY
VARIATIONAL METHODS