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

doi:10.1021/acs.jpca.5b08076

Anion Photoelectron Spectroscopy and CASSCF/CASPT2/RASSI Study of La_n^- (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 La_n^- (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 language	English
Pages (from-to)	11293-11303
Number of pages	11
Journal	Journal of Physical Chemistry A
Volume	119
Issue number	46
DOIs	https://doi.org/10.1021/acs.jpca.5b08076
State	Published - Oct 27 2015
Externally published	Yes

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

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.",

author = "Ivanov, {A. S.} and X. Zhang and H. Wang and Boldyrev, {A. I.} and G. Gantefoer and Bowen, {K. H.} and I. {\v C}ernu{\v s}{\'a}k",

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AU - Ivanov, A. S.

AU - Zhang, X.

AU - Wang, H.

AU - Boldyrev, A. I.

AU - Gantefoer, G.

AU - Bowen, K. H.

AU - Černušák, I.

PY - 2015/10/27

Y1 - 2015/10/27

N2 - 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.

AB - 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.

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ER -

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

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