Dutton Andrew S, Fukuto Jon M, Houk Kendall N
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
Inorg Chem. 2005 May 30;44(11):4024-8. doi: 10.1021/ic048734q.
The complete basis set method, CBS-QB3, is used in combination with two continuum solvation models for aqueous solvation to compute reduction potentials previously determined experimentally for 36 nitrogen oxides and related species of the general formula H(V)C(W)N(X)O(Y)Cl(Z). The PCM model led to the correlation E(o)exp (vs NHE) = 0.84E(o)calc + 0.03 V with an average error of 0.12 V (2.8 kcal/mol) and a maximum error of 0.32 V (7.4 kcal/mol). The CPCM/UAKS model gave E(o)exp (vs NHE) = 0.83E(o)calc + 0.11 V with the same average error. This general method was used to predict reduction potentials (+/-0.3 V) for nitrogen oxides for which reduction potentials are not known with certainty: NO2/NO2- (0.6 V), NO3/NO3- (1.9 V), N2O3-/N2O3(2-) (0.5 V), HN2O3/HN2O3- (0.9 V), HONNO,H+/HONNOH (1.6 V), 2NO,H+/HONNO (0.0 V), 2NO/ONNO- (-0.1 V), ONNO-/ONNO(2-) (-0.4 V), HNO,H+/H2NO (0.6 V), H2NO,H+/H2NOH (0.9 V), HNO,2H+/H2NOH (0.8 V), and HNO/HNO- (-0.7 V).
完整基组方法CBS - QB3与两种用于水相溶剂化的连续介质溶剂化模型相结合，用于计算先前通过实验测定的36种氮氧化物及通式为H(V)C(W)N(X)O(Y)Cl(Z)的相关物种的还原电位。PCM模型得到的相关性为E(o)exp（相对于标准氢电极）= 0.84E(o)calc + 0.03 V，平均误差为0.12 V（2.8千卡/摩尔），最大误差为0.32 V（7.4千卡/摩尔）。CPCM/UAKS模型给出E(o)exp（相对于标准氢电极）= 0.83E(o)calc + 0.11 V，平均误差相同。该通用方法用于预测还原电位不确定的氮氧化物的还原电位（±0.3 V）：NO2/NO2-（0.6 V）、NO3/NO3-（1.9 V）、N2O3-/N2O3(2-)（0.5 V）、HN2O3/HN2O3-（0.9 V）、HONNO,H+/HONNOH（1.6 V）、2NO,H+/HONNO（0.0 V）、2NO/ONNO-（-0.1 V）、ONNO-/ONNO(2-)（-0.4 V）、HNO,H+/H2NO（0.6 V）、H2NO,H+/H2NOH（0.9 V）、HNO,2H+/H2NOH（0.8 V）和HNO/HNO-（-0.7 V）。
