Title: Electronic structure calculations permit identification of the driving forces behind frequency shifts in transition metal monocarbonyls

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/c9cp04643g · OSTI ID:1779233
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Div.; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Div.; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engeering; Univ. of California, Berkeley, CA (United States). Dept. of Bioengineering
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Div.
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We report the adiabatic energy decomposition analysis (EDA) of density functional theory (DFT) results, shedding light on the physical content of binding energies and carbon monoxide (CO) frequency (υCO) shifts in select first-row transition metal monocarbonyls (MCOs; M = Ti-, V-, Cr-, Co-, Ni-, Cu-, V, Cr, Mn, Ni, Cu, Zn, Cr+, Mn+, Fe+, Cu+, and Zn+). This approach allows for the direct decomposition of υCO, in contrast to previous studies of these systems. Neutral, anionic, and cationic systems are compared, and our results indicate that the relative importance of electrostatic interactions, intramolecular orbital polarization, and charge transfer can vary significantly with the charge and electron configuration of the metal participating in binding. Various anomalous systems are also discussed and incorporated into a general model of MCO binding. Electrostatic interactions and orbital polarization are found to promote blue shifts in υCO, while charge transfer effects encourage υCO red-shifting; previously reported values of υCO are found to be a result of a complex but quantifiable interplay between these physical components. Our computations indicate that CuCO- and ZnCO possess triplet ground states, and also that CrCO- exhibits a non-linear geometry, all in contrast to previous computational results. Advantages and limitations of this model as an approximation to more complicated systems, like those implicated in heterogeneous catalysis, are discussed. We also report benchmark results for MCO geometries, binding energies, and harmonic CO frequencies, and discuss the validity of single-reference wave function and DFT approaches to the study of these transition metal systems.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1779233
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 2 Vol. 22; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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