Anion Photoelectron Spectroscopy and CASSCF/CASPT2/RASSI Study of Lan- (n = 1, 3-7)

A. S. Ivanov, X. Zhang, H. Wang, A. I. Boldyrev, G. Gantefoer, K. H. Bowen, I. Černušák

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19 Scopus citations

Abstract

We present a combined experimental and theoretical study of small lanthanum clusters. The experimental photoelectron spectra of Lan- (n = 1, 3-7) were obtained using negative ion photoelectron spectroscopy. Electron affinities for these clusters were found to be in a range of 0.49 eV (La) to 1.5 eV (La7). Our computational tour de force in exploring the electronic structure and its consequences for the lanthanum atom and its anion as well as for lanthanum trimer and its anion shows the multiconfigurational method and large basis set with spin-orbit corrections: CASSCF/CASPT2/RASSI/ANO-RCC-L level of theory is needed to reproduce experimental accuracy. The most stable structure for La3- was established to be an equilateral triangle (1A1′). Chemical bonding analysis of the La3- global minimum reveals that this is the first experimentally observed species with d-AO double σ and π aromaticity.

Original languageEnglish
Pages (from-to)11293-11303
Number of pages11
JournalJournal of Physical Chemistry A
Volume119
Issue number46
DOIs
StatePublished - Oct 27 2015
Externally publishedYes

Funding

FundersFunder number
National Science FoundationCHE-1111693, CHE-1360692, CHE-1361413
National Science Foundation1361413

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