Basis Set Effects in the Description of the Cl-O Bond in ClO and XClO/ClOX Isomers (X = H, O, and Cl) Using DFT and CCSD(T) Methods

Table 6

Enthalpies of formation of ClOCl (in kcal/mol) obtained from reactions (3) and (9)–(14) using the indicated method and the aug-cc-pV6Z basis set. The average value of those obtained for all the reactions and the standard deviation are shown in the last two columns of the table.

Method	(3)	(10)	(9)	(11)	(12)	(13)	(14)	Average	Standard deviation
PW91	17.92	17.10	-2.00	15.79	5.21	33.58	23.00	15.80	11.57
TPSS	18.65	17.99	11.65	19.77	14.35	27.89	22.48	18.97	5.30
B3LYP	19.33	20.55	21.45	24.12	18.46	26.80	21.14	21.69	2.88
PBE0	19.95	21.87	18.24	22.04	19.44	25.84	23.24	21.54	2.57
M06	19.18	20.81	17.55	19.51	20.23	21.47	22.19	20.13	1.55
M06-2X	20.04	19.42	17.41	18.21	18.60	19.01	19.41	18.87	0.88
BMK	20.09	22.29	18.50	20.27	21.29	22.05	23.06	21.08	1.56
B2PLYP	18.90	20.10	19.51	20.70	17.86	21.90	19.06	19.72	1.32
CCSD(T)	19.17	18.45	18.57	18.53	18.73	18.49	18.69	18.66	0.24