Dynamics of electron solvation in I{sup -}(CH{sub 3}OH){sub n} clusters (4 {<=}n{<=} 11)

Journal Article · Mon Mar 28 04:00:00 EDT 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3563720· OSTI ID:21560064

Young, Ryan M; Yandell, Margaret A ^[1]; Neumark, Daniel M ^[1]

---

1. Department of Chemistry, University of California, Berkeley, California 94720 (United States)

The dynamics of electron solvation following excitation of the charge-transfer-to-solvent precursor state in iodide-doped methanol clusters, I{sup -}(CH{sub 3}OH){sub n=4-11}, are studied with time-resolved photoelectron imaging. This excitation produces a I{sup ...}(CH{sub 3}OH){sub n}{sup -} cluster that is unstable with respect to electron autodetachment and whose autodetachment lifetime increases monotonically from {approx}800 fs to 85 ps as n increases from 4 to 11. The vertical detachment energy (VDE) and width of the excited state feature in the photoelectron spectrum show complex time dependence during the lifetime of this state. The VDE decreases over the first 100-400 fs, then rises exponentially to a maximum with a {approx}1 ps time constant, and finally decreases by as much as 180 meV with timescales of 3-20 ps. The early dynamics are associated with electron transfer from the iodide to the methanol cluster, while the longer-time changes in VDE are attributed to solvent reordering, possibly in conjunction with ejection of neutral iodine from the cluster. Changes in the observed width of the spectrum largely follow those of the VDEs; the dynamics of both are attributed to the major rearrangement of the solvent cluster during relaxation. The relaxation dynamics are interpreted as a reorientation of at least one methanol molecule and the disruption and formation of the solvent network in order to accommodate the excess charge.

• OSTI ID: 21560064
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 134; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ALCOHOLS
CHARGE EXCHANGE
DOPED MATERIALS
ELECTRON SPECTROSCOPY
ELECTRON TRANSFER
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
FERMIONS
HALIDES
HALOGEN COMPOUNDS
HALOGENS
HYDROXY COMPOUNDS
IODIDES
IODINE
IODINE COMPOUNDS
LEPTONS
LIFETIME
MATERIALS
METHANOL
MOLECULAR CLUSTERS
MOLECULES
NONMETALS
ORGANIC COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PRECURSOR
RELAXATION
RESOLUTION
SOLVATION
SOLVENTS
SPECTRA
SPECTROSCOPY
TIME DEPENDENCE
TIME RESOLUTION
TIMING PROPERTIES