BROWSE

Related Scientist

Researcher

이효철
나노물질 및 화학반응 연구단
more info

Multireference Ab Initio Study of the Ground and Low-Lying Excited States of Cr(CO)2 and Cr(CO)3

Cited 2 time in webofscience Cited 0 time in scopus
571 Viewed 28 Downloaded
Title
Multireference Ab Initio Study of the Ground and Low-Lying Excited States of Cr(CO)2 and Cr(CO)3
Author(s)
Joonghan Kim; Jeongho Kim; Hyot Cherl Ihee
Publication Date
2013-05
Journal
JOURNAL OF PHYSICAL CHEMISTRY A, v.117, no.187, pp.3861 - 3868
Publisher
AMER CHEMICAL SOC
Abstract
We investigate the ground and low-lying excited states of unsaturated chromium carbonyls, Cr(CO)2 and Cr(CO)3, using multiconfigurational ab initio perturbation theory. Unlike other chromium carbonyls, there are discrepancies between the experiment and theory on the identity of the ground states of Cr(CO)2 and Cr(CO)3. From multireference ab initio calculations considering the full valence orbitals of Cr(CO)2 and Cr(CO)3, the differences in the molecular structures of their various electronic states are explained by the electronic structure analysis. On the basis of the result from CASPT2 and MS-CASPT2 calculations, we propose that the ground states of Cr(CO)2 and Cr(CO)3 are the 5Πg and 1A1 states, respectively, addressing the ambiguity regarding their ground states. In addition, the multiconfigurational ab initio perturbation theory calculations reveal that (1) the energy gaps between the ground and first low-lying excited states of Cr(CO)2 and Cr(CO)3 are quite small and (2) the first low-lying excited states of Cr(CO)2 and Cr(CO)3 have the same spin multiplicities as the ground states of CrCO and Cr(CO)2, respectively, which are the products of ligand dissociation. As a result, the apparent spin-forbidden dissociation of Cr(CO)2 and Cr(CO)3 into CrCO and Cr(CO)2, respectively, are likely to be facilitated by thermal excitation of the ground states of Cr(CO)2 and Cr(CO)3 into their first low-lying excited states, which then actually undergoes the spinallowed dissociation to the ground states of CrCO and Cr(CO)2 with the same spin multiplicities.
URI
https://pr.ibs.re.kr/handle/8788114/1331
ISSN
1089-5639
Appears in Collections:
Center for Nanomaterials and Chemical Reactions(나노물질 및 화학반응 연구단) > Journal Papers (저널논문)
Files in This Item:
19_IBS CA1201-1_Journal of PHYSICAL CHEMISTRY A_177_01_Multireference Ab Initio Study of the Ground and Low-Lying.pdfDownload

qrcode

  • facebook

    twitter

  • Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.
해당 아이템을 이메일로 공유하기 원하시면 인증을 거치시기 바랍니다.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse