skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Experimental and Computational Studies of Alkali-Metal Coinage-Metal Clusters

Abstract

Coinage and alkali metal mixed clusters, M4Na- (M ) Cu, Au) have been investigated experimentally using photoelectron spectroscopy and computationally at correlated ab initio levels. The related Cu4Li-, Ag4 Li-, Ag4Na-, and Au4Li- clusters as well as the neutral Cu4Li2 and Cu4Na2 clusters have also been studied computationally. The calculations show that the two lowest isomers of the negatively charged clusters include a pyramidal C4V structure and a planar C2V species. For Cu4Li- and Cu4Na-, the C4V structure is calculated at correlated ab initio level to be 30.9 and 16.9 kJ/mol below the planar C2V isomer, whereas the planar isomers of Au4Li- and Au4Na- are found to be 29.7 and 49.4 kJ/mol below the pyramidal ones. For Ag4Li- and Ag4Na-, the pyramidal isomers are the lowest ones. Comparison of the calculated and measured photoelectron spectra of Cu4Na- and Au4Na- shows that the pyramidal Cu4Na- cluster of C4V symmetry and the planar Au4Na- of C2V symmetry are detected experimentally. Calculations of the magnetically induced current density in Cu4Li- and Cu4Li2 using the Gauge-Including Magnetically Induced Current (GIMIC) method show that strong ring currents are sustained mainly by the highest-occupied molecular orbital primarily derived from the Cu 4s. The GIMIC calculations thusmore » show that the Cu4 2- ring is ó-aromatic and that the d orbitals do not play any significant role for the electron delocalization effects. The present study does not support the notion that the square-planar Cu4 2- is the first example of d-orbital aromatic molecules.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
882970
Report Number(s):
PNNL-SA-49550
3227a; KP1303000
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry A, 110(12):4244-4250
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Lin, Ying-Chan, Sundholm, Dage, Juselius, Jonas, Cui, Lifeng, Li, Xi, Zhai, Hua-jin, and Wang, Lai S. Experimental and Computational Studies of Alkali-Metal Coinage-Metal Clusters. United States: N. p., 2006. Web. doi:10.1021/jp056789n.
Lin, Ying-Chan, Sundholm, Dage, Juselius, Jonas, Cui, Lifeng, Li, Xi, Zhai, Hua-jin, & Wang, Lai S. Experimental and Computational Studies of Alkali-Metal Coinage-Metal Clusters. United States. doi:10.1021/jp056789n.
Lin, Ying-Chan, Sundholm, Dage, Juselius, Jonas, Cui, Lifeng, Li, Xi, Zhai, Hua-jin, and Wang, Lai S. Thu . "Experimental and Computational Studies of Alkali-Metal Coinage-Metal Clusters". United States. doi:10.1021/jp056789n.
@article{osti_882970,
title = {Experimental and Computational Studies of Alkali-Metal Coinage-Metal Clusters},
author = {Lin, Ying-Chan and Sundholm, Dage and Juselius, Jonas and Cui, Lifeng and Li, Xi and Zhai, Hua-jin and Wang, Lai S.},
abstractNote = {Coinage and alkali metal mixed clusters, M4Na- (M ) Cu, Au) have been investigated experimentally using photoelectron spectroscopy and computationally at correlated ab initio levels. The related Cu4Li-, Ag4 Li-, Ag4Na-, and Au4Li- clusters as well as the neutral Cu4Li2 and Cu4Na2 clusters have also been studied computationally. The calculations show that the two lowest isomers of the negatively charged clusters include a pyramidal C4V structure and a planar C2V species. For Cu4Li- and Cu4Na-, the C4V structure is calculated at correlated ab initio level to be 30.9 and 16.9 kJ/mol below the planar C2V isomer, whereas the planar isomers of Au4Li- and Au4Na- are found to be 29.7 and 49.4 kJ/mol below the pyramidal ones. For Ag4Li- and Ag4Na-, the pyramidal isomers are the lowest ones. Comparison of the calculated and measured photoelectron spectra of Cu4Na- and Au4Na- shows that the pyramidal Cu4Na- cluster of C4V symmetry and the planar Au4Na- of C2V symmetry are detected experimentally. Calculations of the magnetically induced current density in Cu4Li- and Cu4Li2 using the Gauge-Including Magnetically Induced Current (GIMIC) method show that strong ring currents are sustained mainly by the highest-occupied molecular orbital primarily derived from the Cu 4s. The GIMIC calculations thus show that the Cu4 2- ring is ó-aromatic and that the d orbitals do not play any significant role for the electron delocalization effects. The present study does not support the notion that the square-planar Cu4 2- is the first example of d-orbital aromatic molecules.},
doi = {10.1021/jp056789n},
journal = {Journal of Physical Chemistry A, 110(12):4244-4250},
number = ,
volume = ,
place = {United States},
year = {Thu Mar 30 00:00:00 EST 2006},
month = {Thu Mar 30 00:00:00 EST 2006}
}