DFT study on the gas phase reaction of Ni+ with CS2

A theoretical study on the gas phase reaction of Pd+ and Pt+ with CS2

“…This is reasonable and is also confirmed from the bridged C-S bond which is stretched from 1.562 to 1.724 Å. This species is an analogue of those found in the reaction of Ni + with CS 2 [14]. After numerous careful searches, no other earlier encounter complexes or transition states lying before 2 Pt-IM1 were located.…”

“…The binding energy of this complex is 133.9 kJ/mol with a C-S distance of 2.370 Å. Such species was not found for the reaction of Ni + [14]. Interestingly, for the reaction of Pt + ( 2 D, 5d 9 ), a stabilized C-S bridged intermediate complex 2 Pt-IM1 is initially formed and the binding energy of this complex is 176.1 kJ/mol which may be accounted for from the interaction between the p (C-S) orbital and the empty 6s orbital of Pt.…”

“…In Armentrout et al's GIB study on the reaction of Ni + with CS 2 the product NiS + was observed [9], whereas in Cheng et al's study this product was not observed [15]. Our recent study shows that this reaction is highly endothermic and Ni + also exhibits two-state reactivity [14], which indicates that in Cheng et al's study the reaction energy does not meet the threshold energy of this reaction. Naturally, questions will raise here.…”

“…The relative energies calculated at B3LYP, CCSD(T) and QCISD(T) levels are collected in Table 1. For most species, the relative energies at the three levels are close and the applications of these methods in many previous studies on metal and sulfur-containing systems show that they can provide reasonable accurate energetic results [14,16,[27][28][29][30][31][32][33]. Unless otherwise specified, the energies discussed below refer to the results obtained at CCSD (T) level and the potential energy diagrams for the reactions are shown in Figs.…”

“…Moreover, the two-state reactivity (TSR) [10] for the metals is always suggested in these reactions. The following theoretical studies on the reactions have investigated these reactions in detail, and the results of these studies allow us to get more insight into the diversity of the intrinsic reactivity and to gain a better understanding of the similarities and differences observed for the various metals [6,[11][12][13][14]. Recently, Cheng and co-workers reported an experimental study on the reactions of 46 atomic-metal cations with CS 2 at room temperature using inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometry [15].…”