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Chemistry in Nanodroplets: Studies of Protonation Sites of Substituted Anilines in Water Clusters Using FT-ICR

Lee, Sang-Won and Cox, Heather and Goddard, William A., III and Beauchamp, J. L. (2000) Chemistry in Nanodroplets: Studies of Protonation Sites of Substituted Anilines in Water Clusters Using FT-ICR. Journal of the American Chemical Society, 122 (38). pp. 9201-9205. ISSN 0002-7863. doi:10.1021/ja0009875.

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Water clusters of protonated substituted anilines generated by an electrospray ion source have been investigated using a Fourier Transform ion cyclotron resonance mass spectrometer. It is observed that evaporation kinetics and cluster distributions are highly dependent on sites of protonation in the substituted anilines. Based on the examination of the water cluster distributions of protonated aniline derivatives, the site of protonation is postulated to be the amine group for aniline, p-anisidine, p-thiomethylaniline, p-ethylaniline, and m-ethylaniline. The water cluster distributions of these compounds display magic number clusters ([M + nH_2O]+) for n = 20, 27, 50, and 52. However, there is no indication of clusters with special stability for m-anisidine and m-thiomethylaniline, suggesting that these compounds protonate on the ring. DFT calculations have been performed to obtain proton affinities for the different sites of protonation in the substituted anilines and are in good agreement with experimental observation.

Item Type:Article
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URLURL TypeDescription
Goddard, William A., III0000-0003-0097-5716
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 2000 American Chemical Society. Received 20 March 2000. Published online 8 September 2000. Published in print 1 September 2000. The authors are grateful to Dr. Yun Hee Chang for helpful discussions. This work was supported in part by the National Science Foundation under Grant CHE-9727566. Funds for instrument development have been provided by ARPA and the DOD-URI program (ONR-N0014-92-J-1901). H.C. gratefully acknowledges the support of a National Science Foundation graduate research fellowship. We are also indebted to the Beckman Foundation and Institute for the initial funding and continuing support of the research facilities. Computing resources were generously provided by the Material and Process Simulation Center (MSC), also part of the Beckman Institute.
Funding AgencyGrant Number
Advanced Research Projects Agency (ARPA)UNSPECIFIED
Office of Naval Research (ONR)N0014-92-J-1901
NSF Graduate Research FellowshipUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:38
Record Number:CaltechAUTHORS:20170405-115549992
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Official Citation:Chemistry in Nanodroplets:  Studies of Protonation Sites of Substituted Anilines in Water Clusters Using FT-ICR Sang-Won Lee, Heather Cox, William A. Goddard, III, and J. L. Beauchamp Journal of the American Chemical Society 2000 122 (38), 9201-9205 DOI: 10.1021/ja0009875
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75738
Deposited By: Ruth Sustaita
Deposited On:06 Apr 2017 18:02
Last Modified:15 Nov 2021 16:36

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