The Electronic Spectrum of NiCN in the Visible Region

Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

“…This small barrier suggests a relatively low degree of covalency (see Table VI isocyanide bonds. 50,51 On the other hand, as expected, the isomerization barriers corresponding to insertion of the zinc atom into the H-C/N bonds in hydrogen cyanide/isocyanide are rather high (73.13 kcal/mol for the ZnHCN → HZnCN isomerization and 58.61 kcal/mol for the ZnHNC → HZnNC one at the CCSD(T)/aug-cc-pVQZ//CCSD/aug-cc-pVTZ level of theory). Therefore, ZnHCN …”

“…The low isomerization barrier for the HZnNC → HZnCN process (6.41 kcal/mol at the CCSD(T)/aug-cc-pVQZ//CCSD/aug-cc-pVTZ) suggests a relatively low degree of covalency in the metalcyanide/isocyanide bonds. 50,51 Topological analysis of electron density for HZnCN and HZnNC allows us to characterize C-N BCPs as shared interactions typical of covalent compounds. Whereas Zn-C, Zn-N, and Zn-H interactions can be classified as partially covalent closed shell interactions.…”

Ab initio molecular orbital study of ground and low-lying electronic states of NiCN

“…Our predicted equilibrium internuclear distances, r e (Ni-C) = 1.8141 Å and r e (C-N) = 1.1665 Å for the e X 2 D state, computed at the MR-SDCI + Q + E rel /[Roos ANO (Ni), aug-cc-pVQZ(C, N)] level of theory, agree fairly well with the corresponding experimental values: r 0,X=5/2 (Ni-C) = 1.8292(28) Å and r 0,X=5/2 (C-N) = 1.1591(29) Å from Ref. [23], together with r 0 (Ni-C) = 1.8281(6) Å and r 0 (C-N) = 1.1580(8) Å from Ref. [24].…”

“…[23][24][25] are unanimous in concluding that in the electronic ground state e X 2 D 5=2 , NiCN is linear at equilibrium. Experimentally for the e X 2 D state, Kingston et al [23] obtained the geometrical parameter values (quantities in parentheses are quoted uncertainties in units of the last digit given) r 0,X=5/2 (Ni-C) = 1.8292(28) Å , r 0,X=5/2 -(C-N) = 1.1591(29) Å , and B 0,5/2 = 0.1444334(30) cm À1 , while Sheridan and Ziurys [24] determined r 0,X=5/2 (Ni-C) = 1.8293(1) Å (r 0 (Ni-C) = 1.8281(6) Å ), r 0,X=5/2 (C-N) = 1.1590(2) Å (r 0 (C-N) = 1.1580(8) Å ), and B 0,5/2 = 0.144435153(53) cm À1 . The reader should note the excellent agreement between these two sets of experimental results.…”

“…It has already been investigated extensively in laser-induced-fluorescence (LIF) experiments by Kingston et al [23], in pure rotational-spectroscopy experiments by Sheridan and Ziurys [24] and theoretically, in ab initio calculations, by Paul et al [25]. In addition, there are two earlier ab initio studies by Bauschlicher [26] and by Zhou et al [27] on NiCN as a model for CN adsorbed on nickel metal surface.…”