Issue 19, 2012

Investigation of spin-flip reactions of Nb + CH3CN by relativistic density functional theory

Abstract

In order to explore the details of the reaction mechanisms of Nb atoms with acetonitrile molecules, the sextet, quartet, and doublet spin state potential energy surfaces have been investigated. Density functional theory (DFT) with the relativistic zero-order regular approximation at the PW91/TZ2P level has been applied. The complicated minimum energy reaction path involves four transition states (TS), stationary states (1) to (5) and two intersystem crossings from spin sextets to quartets to doublets (indicated by ⇒): 6Nb + NCCH36Nb η1-NCCH3 (61) → 6TS1/24Nb η2-(NC)CH3 (42) → 4TS2/34NbH η3-(NCCH2) (43) → 4TS3/4 → CNNbCH3 (44) ⇒ 2TS4/5 → CN(NbH)CH2 (25). The minimum energy crossing points were determined with the help of the DFT fractional-occupation-number approach. The first spin inversion leads from the sextet to an energetically low intermediate quartet (42) with final insertion of Nb into the C–C bond. The second one from the quartet to the doublet state facilitates the activation of a C–H bond, lowering the rearrangement-barrier by 44 kJ mol−1. The overall reaction is calculated to be exothermic by about 170–180 kJ mol−1. All intermediate and product species were frequency and NBO analyzed. The species can be rationalized with the help of Lewis type formulas.

Graphical abstract: Investigation of spin-flip reactions of Nb + CH3CN by relativistic density functional theory

Supplementary files

Article information

Article type
Paper
Submitted
13 Oct 2011
Accepted
21 Mar 2012
First published
22 Mar 2012

Phys. Chem. Chem. Phys., 2012,14, 6833-6841

Investigation of spin-flip reactions of Nb + CH3CN by relativistic density functional theory

Q. Li, Y. Qiu, X. Chen, W. H. E. Schwarz and S. Wang, Phys. Chem. Chem. Phys., 2012, 14, 6833 DOI: 10.1039/C2CP23225A

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