A density functional study on interaction of first-row transition-metal dicarbides, C2X (X=Sc-Zn) with O2by Saroj K. Parida, Sridhar Sahu, Sagar Sharma

Chemical Physics Letters


Physical and Theoretical Chemistry / Physics and Astronomy (all)


Chemical Physics Letters 626 (2015) 1–5

Contents lists available at ScienceDirect

Chemical Physics Letters jou rn al hom epage: www.elsev ier .com/ locate /cp le t t

A density functional study on interaction of firstdicarbi

Saroj K. P a Department o b Department o a r t i c l

Article history:

Received 18 D

In final form 2

Available onlin den icarb ed w ical an most with 1. Introdu

Since la involving fi ments have prospective alysts, elect the discovery of carbide chains doped with first- and second-row elements in interstellar media, a lot of theoretical and experimental works have been reported exploring the adsorption of other elements specifically TMs on these clusters. For example, Roszak et al. comp using correl

C2v structur provided by lated the str many-body 3B1 state [12 on the struc [13,14]. Mo using densi most favore et al., using

FeC2 and Fe 5A1 state w ∗ Correspon

E-mail add 1 Present Ad ence and Tech ral a

SDT 1) cy g me have eve s sm 2 2 tigated thoroughly [21,22]. H2 adsorption on alkali metal (Li, Na) terminated carbon chains has been investigated theoretically by Liu et al. [23]. Similarly, theoretical work of Moras et al. showed that the chemisorption of O2 molecules on carbon chains resulted in cleavhttp://dx.doi.o 0009-2614/© uted the structural and electronic properties of ScC2 ation consistent ab initio methodologies and obtained a e which closely matched with the experimental results

Haque et al. [10,11]. Similarly, Sumathi et al. calcuuctural and electronic properties of TiC2 using ab initio methods and found a C2v ground state geometry with ]. Largo et al. reported their extensive theoretical works tural and electronic properties of VCn and ZnCn clusters reover, Barrientos et al. investigated structures of TiCn ty functional theory (DFT) and found fan isomers to be d for small-sized clusters [15,16]. Similarly, Hendrickx ab inito approach, explored the structure and bonding of

C3 clusters and noted that for FeC2, a C2v structure with as most stable [17,18]. Similarly, electronic structures ding author. ress: sridharsahu@gmail.com (S. Sahu). dress: Physical Sciences Division,Institute of Advanced Study in Scinology,Paschim Boragaon, Guwahati 781035, Assam, India. age and shortening of the carbynoid structures [24]. Dibben et al. performed both theoretical and experimental work to investigate the interaction of linear carbon clusters with water molecule and revealed the photoproduction of CnO compound from the Cn.H2O complexes [25]. Furthermore, Eichelberger et al. performed experimental investigation on the reactivity of ionic carbon chains with

H, N, and O atoms and found that the ionic chains are more reactive towards O than H and N [26]. However, only a handful of investigation focusing on the reactivity profile of heteroatom-doped carbon chains have been performed [27,28]. In this letter we present our theoretical study of interaction of first-row transition-metal dicarbides with O2 molecule. 2. Computation

For the present study, all the structures were optimized within the framework of density-functional theory (DFT). In particular, we used Becke’s three-parameter hybrid exchange functional and Lee–Yang–Parr correlation functional employing triple split-valence basis set 6-311+G(3df) which includes diffuse and rg/10.1016/j.cplett.2015.03.005 2015 Elsevier B.V. All rights reserved.des, C2X (X = Sc-Zn) with O2 aridaa, Sridhar Sahua,∗, Sagar Sharmab,1 f Applied Physics, Indian School of Mines, Dhanbad, Jharkhand 826004, India f Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel e i n f o ecember 2014

March 2015 e 12 March 2015 a b s t r a c t

We present our calculations based on

O2 on the first-row transition-metal d be less in C2XO2 (X = Sc-V) as compar amount of total charge on O2. Topolog

V) is prominent between X and O and

C O and X O bondings are observed ction st many years, hetero-atom doped carbon clusters rst-row, second-row and transition metal (TM) eleacquired meticulous attention due to their enormous applications such as hydrogen storage, chemical catronic devices, superconductors and so on [1–9]. Since of neut and CC and 6A bondin metals

How towardrow transition-metal sity functional theory to explore the molecular adsorption of ides C2X (X = Sc-Zn). Degree of activation of O2 is observed to ith C2XO2 (X = Cr-Zn) except for X = Cu, and is marked by the alysis shows that the interaction in the cases of C2XO2 (X = Scly being intermediate type whereas in C2XO2 (X = Cr-Zn), both shared-kind and intermediate characteristics respectively. © 2015 Elsevier B.V. All rights reserved. nd ionic MnC2 was studied by Tran et al. using both DFT (T) methodologies, who obtained high-spin states (7A1 clic isomers to be stable structures [19]. Moreover, the chanisms in dicarbides doped with first-row transition also been discussed in detail by Largo et al. [20]. r, except a few reports, reactivity of carbon chains all molecules such as O , CO, CO etc. are yet to be inves2 S.K. Parida et al. / Chemical Physics Letters 626 (2015) 1–5 polarization functions and Wachters-Hay basis set with scaling factor of Raghavachari and Trucks designed for the first-row transition metal elements [30–33,29]. As effective core potential basis sets of double-zeta (DZ) quality such as Los Alamos National Laboratory (LANL2DZ) ters contain the variatio 6-311++G(d

As the su system spec exchange fu corrected c gradient-co

Ernzerhof ( both the ca clusters we sible sites o without an ering the fa show high(without an this work, o discussed. G and Chemc lations [36,

O2 molecul function (E using Top-M [38,39]. 3. Results 3.1. Structu

In Figure ters, with X in general, u been provid except C2C with O2 mo is observed from the fig dicarbides d with those the former molecule, w metals take

We prov

O O bond l clusters in of theory h bond length at B3LYP/L with other in the case and decrea decrease (4