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 3

Standard enthalpies of formation of HClO (in kcal/mol) obtained from the reaction of atomization and reactions (3), (4), (7), and (8) are reported in the first five columns of the table. The energy difference between HClO and HOCl (without zero-point energies) is shown in the sixth column. The last column shows the average of the enthalpies of formation calculated using reactions of atomization, (4), (7), and (8). Values obtained with reaction (3) were not included in this average. The last file shows the averages, for each reaction, of the values of the enthalpy of reaction obtained with each method, excluding the PW91 and TPSS values.

	Reaction					ΔE
	TAE	(4)	(8)	(7)	(3)	HClO-HOCl	Average
PW91	16.3	29.7	37.4	33.7	12.0	48.1	29.3
TPSS	26.6	33.3	34.6	34.4	3.5	48.6	32.2
B3LYP	33.1	34.2	32.1	33.8	6.5	51.7	33.3
PBE0	32.3	32.8	34.4	33.8	32.4	50.6	33.3
M06	31.9	32.5	35.8	33.3	19.5	51.8	33.4
M06-2X	33.7	34.2	30.1	33.1	20.4	54.3	32.8
BMK	34.9	36.3	31.6	35.8	23.1	55.0	34.6
B2PLYP	32.9	33.9	37.2	32.5	21.3	54.8	34.2
CBS-QB3	32.3	34.0	35.8	32.5	34.7	51.6	33.7
G4	33.9	33.6	34.7	31.8	34.8	51.6	33.5
W1BD		32.7	34.7	33.1	34.4	51.6	33.5
CCSD(T)	33.5	33.1	34.5	33.0	40.6	53.5	33.5
Average	33.2	33.7	34.1	33.3	26.8