TY - JOUR
T1 - Solvation effects on angular distributions in H-(NH 3)n and NH2-(NH3) n photodetachment
T2 - Role of solute electronic structure
AU - Grumbling, Emily R.
AU - Sanov, Andrei
N1 - Funding Information:
We thank Kostyantyn Pichugin for assistance with experiments at early stages of this project and comments on the manuscript prior to publication. This work is supported by the U.S. National Science Foundation (Grant CHE-1011895).
PY - 2011/10/28
Y1 - 2011/10/28
N2 - We report 355 and 532 nm photoelectron imaging results for H -(NH3)n and NH2-(NH 3)n, n=0-5. The photoelectron spectra are consistent with the electrostatic picture of a charged solute (H- or NH 2-) solvated by n ammonia molecules. For a given number of solvent molecules, the NH2- core anion is stabilized more strongly than H-, yet the photoelectron angular distributions for solvated H- deviate more strongly from the unsolvated limit than those for solvated NH2-. Hence, we conclude that solvation effects on photoelectron angular distributions are dependent on the electronic structure of the anion, i.e., the type of the initial orbital of the photodetached electron, rather than merely the strength of solvation interactions. We also find evidence of photofragmentation and autodetachment of NH2-(NH3)2-5, as well as autodetachment of H-(NH3)5, upon 532 nm excitation of these species.
AB - We report 355 and 532 nm photoelectron imaging results for H -(NH3)n and NH2-(NH 3)n, n=0-5. The photoelectron spectra are consistent with the electrostatic picture of a charged solute (H- or NH 2-) solvated by n ammonia molecules. For a given number of solvent molecules, the NH2- core anion is stabilized more strongly than H-, yet the photoelectron angular distributions for solvated H- deviate more strongly from the unsolvated limit than those for solvated NH2-. Hence, we conclude that solvation effects on photoelectron angular distributions are dependent on the electronic structure of the anion, i.e., the type of the initial orbital of the photodetached electron, rather than merely the strength of solvation interactions. We also find evidence of photofragmentation and autodetachment of NH2-(NH3)2-5, as well as autodetachment of H-(NH3)5, upon 532 nm excitation of these species.
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U2 - 10.1063/1.3653232
DO - 10.1063/1.3653232
M3 - Article
C2 - 22047233
AN - SCOPUS:80555139810
SN - 0021-9606
VL - 135
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 16
M1 - 164301
ER -