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Structure and Stability of Palladium−Carbon Cations

Strout, Douglas L. and Miller, Thomas F., III and Hall, Michael B. (1998) Structure and Stability of Palladium−Carbon Cations. Journal of Physical Chemistry A, 102 (31). pp. 6307-6310. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20130301-153144543

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Abstract

A theoretical study has been carried out to explore various isomers of palladium−carbon cations, PdC_x^+. By using the B3LYP density functional method, the geometries have been optimized for linear PdC_x+ as well as several classes of cyclic, bicyclic, and graphitic isomers. Linear clusters are shown to be the most stable isomers for x < 10, which is contrary to the previously studied behavior of lanthanum, an early transition metal. For larger systems, several classes of ring-containing structures are more stable than the linear isomers. Experimental ion mobility studies of the PdC_x^+ clustering process reveal monocyclic rings for x > 10, a result consistent with the B3LYP prediction of rings as the most stable isomer. The ion mobility experiments did not produce any results for x < 10, which may be due to the reactivity of the linear PdC_x^+, which are predicted by B3LYP to be the most stable isomers at those sizes. Bicyclic PdC_(20)^+ is shown to be less stable than the monocyclic rings, but the appearance of bicyclic PdC_(20)^+ in the ion mobility experiments is explained as the result of binary collisions since it is stable with respect to PdC_(10)^+ and C_(10) rings. Graphitic PdC_(20)^+ is shown to be more stable than either monocyclic or bicyclic rings, although the graphitic sheets do not appear in the ion mobility experiments until PdC_(26)^+.


Item Type:Article
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http://dx.doi.org/10.1021/jp980640c DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp980640cPublisherArticle
ORCID:
AuthorORCID
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 1998 American Chemical Society. Received: January 6, 1998; In Final Form: May 15, 1998. Published on Web 07/01/1998. We thank the National Science Foundation (Grant Nos. CHE 94-23271 and CHE 95-28196) and the Robert A. Welch Foundation (Grant No. A-648) for financial support. We thank a reviewer for pointing out the possible connection between the low stability for fan structures and endohedral fullerenes.
Funders:
Funding AgencyGrant Number
NSFCHE 94-23271
NSFCHE 95-28196
Robert A. Welch FoundationA-648
Record Number:CaltechAUTHORS:20130301-153144543
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20130301-153144543
Official Citation:Structure and Stability of Palladium−Carbon Cations Douglas L. Strout,Thomas F. Miller III, and, and Michael B. Hall The Journal of Physical Chemistry A1998102 (31), 6307-6310
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:37258
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:04 Mar 2013 23:57
Last Modified:30 Jan 2017 22:34

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