Density functional and Ab initio study of Cr(CO)n (n = 1-6) complexes

Joonghan Kim, Tae Kyu Kim, Jangbae Kim, Yoon Sup Lee, Hyotcherl Ihee

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Cr(CO)n (n = 1-6) systems were studied for all possible spin states using density functional and high-level ab initio methods to provide a more complete theoretical understanding of the structure of species that may form during ligand dissociation of Cr(CO)6. We carried out geometry optimizations for each system and obtained vibrational frequencies, sequential bond dissociation energies (BDE), and total CO binding energies. We also compared the performance of various DFT functionals. Generally, the ground states of Cr(CO)6, Cr(CO)5, and Cr(CO)4, whose spin multiplicity is a singlet, are in good agreement with both previous theoretical results and currently available experimental data. Calculations on Cr(CO)3, Cr(CO)2, and CrCO provide new findings that the ground state of Cr(CO)3 might be a quintet with C2v symmetry instead of a singlet with C3v symmetry, and the ground state of Cr(CO)2 is not a linear quintet, as suggested by previous DFT calculations, but rather a linear septet. We also found that nonet states of Cr(CO)2 and CrCO display partial C-O bond breakage.

Original languageEnglish
Pages (from-to)4697-4710
Number of pages14
JournalJournal of Physical Chemistry A
Volume111
Issue number21
DOIs
Publication statusPublished - 2007 May 31

Fingerprint

Ground state
Discrete Fourier transforms
ground state
dissociation
Crystal symmetry
symmetry
Vibrational spectra
Binding energy
functionals
binding energy
Ligands
ligands
optimization
Geometry
geometry
energy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Kim, Joonghan ; Kim, Tae Kyu ; Kim, Jangbae ; Lee, Yoon Sup ; Ihee, Hyotcherl. / Density functional and Ab initio study of Cr(CO)n (n = 1-6) complexes. In: Journal of Physical Chemistry A. 2007 ; Vol. 111, No. 21. pp. 4697-4710.
@article{3d5a6105e1de401cb4c38ffcc540b28d,
title = "Density functional and Ab initio study of Cr(CO)n (n = 1-6) complexes",
abstract = "Cr(CO)n (n = 1-6) systems were studied for all possible spin states using density functional and high-level ab initio methods to provide a more complete theoretical understanding of the structure of species that may form during ligand dissociation of Cr(CO)6. We carried out geometry optimizations for each system and obtained vibrational frequencies, sequential bond dissociation energies (BDE), and total CO binding energies. We also compared the performance of various DFT functionals. Generally, the ground states of Cr(CO)6, Cr(CO)5, and Cr(CO)4, whose spin multiplicity is a singlet, are in good agreement with both previous theoretical results and currently available experimental data. Calculations on Cr(CO)3, Cr(CO)2, and CrCO provide new findings that the ground state of Cr(CO)3 might be a quintet with C2v symmetry instead of a singlet with C3v symmetry, and the ground state of Cr(CO)2 is not a linear quintet, as suggested by previous DFT calculations, but rather a linear septet. We also found that nonet states of Cr(CO)2 and CrCO display partial C-O bond breakage.",
author = "Joonghan Kim and Kim, {Tae Kyu} and Jangbae Kim and Lee, {Yoon Sup} and Hyotcherl Ihee",
year = "2007",
month = "5",
day = "31",
doi = "10.1021/jp066081o",
language = "English",
volume = "111",
pages = "4697--4710",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "21",

}

Density functional and Ab initio study of Cr(CO)n (n = 1-6) complexes. / Kim, Joonghan; Kim, Tae Kyu; Kim, Jangbae; Lee, Yoon Sup; Ihee, Hyotcherl.

In: Journal of Physical Chemistry A, Vol. 111, No. 21, 31.05.2007, p. 4697-4710.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Density functional and Ab initio study of Cr(CO)n (n = 1-6) complexes

AU - Kim, Joonghan

AU - Kim, Tae Kyu

AU - Kim, Jangbae

AU - Lee, Yoon Sup

AU - Ihee, Hyotcherl

PY - 2007/5/31

Y1 - 2007/5/31

N2 - Cr(CO)n (n = 1-6) systems were studied for all possible spin states using density functional and high-level ab initio methods to provide a more complete theoretical understanding of the structure of species that may form during ligand dissociation of Cr(CO)6. We carried out geometry optimizations for each system and obtained vibrational frequencies, sequential bond dissociation energies (BDE), and total CO binding energies. We also compared the performance of various DFT functionals. Generally, the ground states of Cr(CO)6, Cr(CO)5, and Cr(CO)4, whose spin multiplicity is a singlet, are in good agreement with both previous theoretical results and currently available experimental data. Calculations on Cr(CO)3, Cr(CO)2, and CrCO provide new findings that the ground state of Cr(CO)3 might be a quintet with C2v symmetry instead of a singlet with C3v symmetry, and the ground state of Cr(CO)2 is not a linear quintet, as suggested by previous DFT calculations, but rather a linear septet. We also found that nonet states of Cr(CO)2 and CrCO display partial C-O bond breakage.

AB - Cr(CO)n (n = 1-6) systems were studied for all possible spin states using density functional and high-level ab initio methods to provide a more complete theoretical understanding of the structure of species that may form during ligand dissociation of Cr(CO)6. We carried out geometry optimizations for each system and obtained vibrational frequencies, sequential bond dissociation energies (BDE), and total CO binding energies. We also compared the performance of various DFT functionals. Generally, the ground states of Cr(CO)6, Cr(CO)5, and Cr(CO)4, whose spin multiplicity is a singlet, are in good agreement with both previous theoretical results and currently available experimental data. Calculations on Cr(CO)3, Cr(CO)2, and CrCO provide new findings that the ground state of Cr(CO)3 might be a quintet with C2v symmetry instead of a singlet with C3v symmetry, and the ground state of Cr(CO)2 is not a linear quintet, as suggested by previous DFT calculations, but rather a linear septet. We also found that nonet states of Cr(CO)2 and CrCO display partial C-O bond breakage.

UR - http://www.scopus.com/inward/record.url?scp=34250320953&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34250320953&partnerID=8YFLogxK

U2 - 10.1021/jp066081o

DO - 10.1021/jp066081o

M3 - Article

C2 - 17488098

AN - SCOPUS:34250320953

VL - 111

SP - 4697

EP - 4710

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 21

ER -