Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	The activation of carbon dioxide by first row transition metals (Sc-Zn)
Δημιουργός/Συγγραφέας:	Blaziak K. [EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter Xantheas S.S. Uggerud E.
Εκδότης:	Royal Society of Chemistry
Ημερομηνία:	2018
Γλώσσα:	Αγγλικά
ISSN:	1463-9076
DOI:	10.1039/c8cp04231d
Άλλο:	PubMed ID: 30276383
Περίληψη:	The activation of CO2 by chloride-tagged first-row transition metal anions [ClM]- (M = Sc-Zn), was examined by mass spectrometry, quantum chemical calculations, and statistical analysis. The direct formation of [ClM(CO2)]- complexes was demonstrated in the reaction between [ClM]- and neutral CO2. In addition, the reverse reaction was investigated by energy-variable collisionally induced dissociation (CID) of the corresponding [ClM(CO2)]- anions generated in-source. Five different mono- A nd bi-dentate binding motifs present in the ion/CO2 complexes were identified by quantum chemical calculations and the relative stability of each of these isomers was established and analyzed for all first-row transition metals based on the experimental and theoretical ion/molecule binding energies. It was found that the early first row transition metals form strong covalent bonds with the neutral CO2 molecule, while the late ones and in particular copper and zinc are weakly bonded. Using simple valence bond Lewis diagrams, the different binding motifs and their relative stabilities across the first row were described using multi-configurational self consistent field (MSCSCF) wavefunctions in a quantitative manner based on the electronic structure of the individual metals. This analysis provides an explanation for the change of the most favorite bonding motif of the transition metals with CO2 along the 1st transition metal row. The nature of the activated CO2 complex and the relationship between its stability and other structural and spectral properties was also analyzed by Principal Component Analysis (PCA) and artificial neural networks.
Τίτλος πηγής δημοσίευσης:	Physical Chemistry Chemical Physics
Τόμος/Κεφάλαιο:	20
Τεύχος:	39
Σελίδες:	25495-25505
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry
Αξιολόγηση από ομότιμους (peer reviewed):	Ναι
Κάτοχος πνευματικών δικαιωμάτων:	© the Owner Societies.
Σημειώσεις:	NN4654K; U.S. Department of Energy, USDOE; Office of Science, SC; Basic Energy Sciences, BES; Pacific Northwest National Laboratory, PNNL; Chemical Sciences, Geosciences, and Biosciences Division, CSGB; National Energy Research Scientific Computing Center, NERSC: DE-AC02-05CH11231; Norges Forskningsråd: 249788, 262695/F50 This work was supported by the Norwegian Research Council through Grant No. 249788, The chemistry of CO2 activation and fixation; to the Hylleraas Centre for Quantum Molecular Sciences No. 262695/F50 through their Centre of Excellence program, and the Norwegian Supercomputing Program (NOTUR) through a grant of computer time (Grant No. NN4654K). SSX acknowledges support from the Center for Scalable Predictive methods for Excitations and Correlated phenomena (SPEC), which is funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, as part of the Computational Chemical Sciences Program at Pacific Northwest National Laboratory. Battelle operates the Pacific Northwest National Laboratory for the U.S. Department of Energy. This research also used computer resources provided by the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The authors are indebted to Prof. Witold Danikiewicz for providing access to the mass spectrometry facility at the Institute of Organic Chemistry, Polish Academy of Sciences, and for scientific advice.
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο