Fourier Transform Microwave Spectroscopy of Cyanides and Isocyanides of Al, Ga, and In

A theoretical study of FeNC in the 6Δ electronic ground state

“…Our calculations also indicate that the second approximation of a linear r 0 -structure is a serious one, responsible for the unreasonable value of r 0 (N-C) obtained in [1]. This conclusion is supported by previous work [38][39][40][41]. In particular, Lide and Kuczkowski [38] showed that they could 'cure' an analogous anomaly found for CsOH and CsOD by including in the analysis experimentally available B-values for excited bending states and thus removing the influence on r 0 from the large-amplitude bending motion.…”

“…Conclusions analogous to ours have been reached by other workers [38][39][40][41]. For example, Lide and Kuczkowski [38] found already in 1967 that the r 0 -structure for CsOH, determined from the B 0 values of CsOH and CsOD, had a ''suspiciously short'' OH bond length because of the large-amplitude bending motion.…”

“…From the extrapolated, bending-less B values, they obtained reasonable bond lengths 3 for CsOH. Much more recently, Walker et al [41] have shown that to get such reasonable structures for the cyanides and isocyanides of Al, Ga, and In, they had to fit their rotational spectra in terms of a rigid-bender model explicitly describing the bending motion while neglecting the stretching motion.…”

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

“…However, it should be noted in this point that the flat bending in cyanides may lead to the prediction of somewhat short C-N distances from the experimental data. [55][56][57][58][59][60] Finally, as it can be inferred from Table III, the C-N bond distances in isomers with a cyanide arrangement are slightly shorter than that in cyanogen (1.1705 Å at CCSD(T)/aug-ccpVQZ level). And the opposite is true for the corresponding isomers with an isocyanide arrangement.…”

A theoretical study of FeCN in the 6Δ electronic ground state

“…[31][32][33][34][35]), and all the molecules mentioned above have relatively shallow bending potentials that give rise to large-amplitude bending motion. Thus, in addition to the aim of guiding experimental work on the molecules studied and facilitating the analysis of experimental results, our theoretical studies of metal cyanides and isocyanides acquire a further purpose: To provide accurate structural information, in particular accurate bond length values to supersede the experimentally derived, too-short values.…”