关键词:
ab initio computations
chemical shift computations
Ga-71
electric field gradient
摘要:
Ga-71 chemical shifts computed with the GIAO (gange-including atomic orbitals)-SCF method and medium-sized basis sets for optimized geometries are reported for GaMe(3), GaMe(3)-NMe(3), GaCl4-, Ga2Cl6, Ga(OH4)(-), GaH4-, Ga(OH2)(3)(3+), Ga(NCMe)(6)(3+), Ga(C(5)Me(5)), Ga[GaCl4] and Ga(C5H5). Experimental trends are well reproduced, but the slope of the delta(calc) vs. delta(exp) correlation is only 0.93 instead of unity. For selected compounds, the electron-correlated GIAO-MP2, method affords an improved description of the chemical shift range covered (ca. 1400 ppm). Geometry effects on delta(Ga-71) are small in most cases, but can be notable for certain Ga-I species, e.g. for Ga-I[GaCl4], the calculated Ga-I chemical shift of which also depends strongly on aggregation and solvation. delta(Ga-71) values no larger than 153 ppm are computed for LiGaH4 and aggregates thereof, in sharp contrast to the published experimental value of 682 ppm. Based on accurate GIAO-CCSD(T) calculations (at a highly correlated coupled-cluster level), a delta(Ga-71) value of ca. 615 ppm is predicted for GaH3. At the GIAO-MP2 level, delta(Ga-71) = 312 ppm is predicted for GaMe(4)(-), which should be accessible experimentally. The computed sigma(Ga) values in the most strongly shielded Ga-I species approach that of isolated Ga+. Since sigma(Ga) of isolated Ga3+ is similar, the deshielding in molecules containing Ga-III is attributed to large paramagnetic contributions of the bonding MOs in the valence shell. For a number of molecules, trends in experimental delta(Ga-71) linewidths can be rationalized in terms of the relative magnitudes of the electric field gradient at the Ga atom.