Table IV

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Table IV. Calculated (W[Q5;Q5;TQ5] level) and experimental total atomization energies (kcal/mol).

	SCF limit	CCSD(T) val.	Inner-shell	Expmtl.	Scalar relativ.	Best calc.	Error in	Experimental	Experimental	Zero-Point	Experimental
	(TQ5 extr.)	Corr. limit	correlation	spin-orbit	effects	Total Atomiz.	calculated	TAE_e [e]	error	Vibrational	TAE₀
		(Q5 extr.)	CCSD(T) [c]	splitting	ACPF [d]	Energy (TAE)	TAE's			Energies [m]

H₂	83.85	25.68	0.00	0.00	0.00	109.53	0.05	109.48	0.00 [f]	6.21	103.27
N₂	119.67	107.72	0.75	0.00	-0.12	228.03	-0.39	228.42	0.04 [f]	3.36	225.06
O₂	26.76	93.20	0.24	-0.45	-0.16	119.60	-0.62	120.22	0.04 [f]	2.25	117.97
F₂	-31.09	69.55	-0.09	-0.77	0.03	37.63	-0.61	38.24	0.10 [f]	1.30	36.94
HF	100.03	41.52	0.18	-0.39	-0.20	141.15	-0.03	141.18	0.17 [f]	5.85	135.33
CH	57.22	26.73	0.14	-0.04	-0.04	84.01	0.07	83.94	0.23 [f]	4.04	79.90
CO	181.84	76.89	0.94	-0.31	-0.14	259.21	-0.06	259.27	0.12 [g]	3.11	256.16
NO	54.90	97.01	0.40	-0.05	-0.17	152.09	-0.44	152.54	0.03 [g]	2.71	149.82
CS	104.15	67.01	0.75	-0.64	-0.16	171.11	-0.33	171.45	0.23 [f]	1.83	169.41
SO	53.12	72.84	0.46	-0.78	-0.32	125.32	0.09	125.22	0.04 [f]	1.64	123.58
HCl	80.86	26.62	0.20	-0.84	-0.26	106.57	0.09	106.48	0.02 [f]	4.24	102.24
ClF	15.38	47.29	0.08	-1.23	-0.14	61.39	-0.08	61.48	0.01 [f]	1.12	60.36
Cl₂	26.84	33.05	0.19	-1.68	-0.18	58.22	0.25	57.98	0.00 [f]	0.80	57.18
HNO	85.42	119.67	0.40	-0.22	-0.25	205.03	-0.38	205.41	0.06 [h]	8.56	196.85
CO₂	258.05	130.29	1.64	-0.53	-0.46	389.00	-0.15	389.15	0.06 [g]	7.24	381.91
H₂O	160.01	72.73	0.37	-0.22	-0.26	232.62	0.02	232.60	0.12 [g]	13.25	219.35
H₂S	133.64	50.03	0.34	-0.56	-0.41	183.04	0.44	182.60	0.12 [i]	9.40 [n]	173.15
HOCl	86.67	79.38	0.31	-1.06	-0.30	165.00	0.18	164.81	0.12 [i]	8.21 [o]	156.61
OCS	218.24	116.09	1.68	-0.87	-0.54	334.60	0.36	334.24	0.48 [i]	5.72 [k]	328.53
ClCN	169.49	114.31	1.76	-0.93	-0.44	284.20	-0.32	284.52	0.48 [i]	5.33 [p]	279.20
SO₂[a]	122.06	137.61	0.67	-1.01	-0.71	258.62	0.23	258.39	0.08 [i]	4.38 [a]	253.92
CH₃	243.43	63.42	1.04	-0.08	-0.17	307.63	0.19	307.44	0.10 [j]	18.44 [q]	289.00
NH₃	203.28	94.19	0.62	0.00	-0.25	297.84	-0.22	298.06	0.13 [g]	21.33	276.73
PH₃	173.23	68.63	0.30	0.00	-0.47	241.69	0.13	241.56	0.41 [k]	14.44 [r]	227.13
C₂H₂	299.88	103.15	2.44	-0.17	-0.27	405.02	-0.34	405.36	0.24 [l]	16.46	388.90
H₂CO	264.82	108.53	1.25	-0.31	-0.32	373.98	0.15	373.82	0.12 [i]	16.53	357.25
CH₄	331.58	87.67	1.21	-0.08	-0.19	420.20	0.09	420.11	0.14 [k]	27.60	392.51
C₂H₄[b]	435.07	126.84	2.36	-0.17	-0.33	563.77	0.26	563.51	0.17 [k]	31.60	531.91

a) The geometry and zero point energy are from J. M. L. Martin, J. Chem. Phys. 108 (1998) 2791.

b) The geometry and zero point energy are from J. M. L. Martin and P. R. Taylor, Chem. Phys. Lett. 248 (1996) 336. Valence energies were obtained with VnZ set.

c) The basis sets were acv5z for most first-row molecules and MTavqz for most second-row.

For SO₂, CH₃, NH₃, C₂H₂, H₂CO, CH₄ and C₂H₄, the MT basis set was used.

d) The basis sets were acvqz for most first-row molecules and MTavqz for most second-row.

For SO₂, CH₃, NH₃, C₂H₂, H₂CO, CH₄ and C₂H₄, the MT basis set was used.

e) This "bottom of the well" value was obtained by adding the experimental TAE_0 to the best available zero point vibration energy.

f) K. P. Huber and G. Herzberg, "Constants of Diatomic Molecules" (Van Nostrand Reinhold, New York, 1979).

g) J. D. Cox, D. D. Wagman, and V. A. Medvedev, CODATA key values for thermodynamics (Hemisphere, New York, 1989).

h) R. N. Dixon, J. Chem. Phys. 104, 6905 (1996).

i) L. V. Gurvich, I. V. Veyts, and C. B. Alcock (Eds.), Thermodynamic properties of individual substances, 4th Ed. (Hemisphere, New York, 1989).

j) J. M. L. Martin, Chem. Phys. Lett. 273, 98 (1997).

k) NIST-JANAF Thermochemical Tables, 4th Edition, Ed. M. W. Chase Jr., J. Phys. Chem. Ref. Data Monograph 9 (1998).

l) D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow, S. M. Bailey, K. L. Churney, and R. L. Nuttall, J. Phys. Chem. Ref. Data 11, supplement 2 (1982).

m) ZPVE for diatomics were derived from spectroscopic constants in [f], while those for polyatomics were taken from [h]

n) I. Kozin and P. Jensen, J. Mol. Spec. 163 (1994) 483.

o) B. Abel, H.H. Hamann, A.A. Kachanov, and J. Troe, J. Chem. Phys. 104 (1996) 3189.

p) T.J. Lee, J.M.L. Martin, C.E. Dateo and P. R. Taylor, J. Phys Chem. 99 (1995) 15858.

q) Taken from from unpublished work of D. W. Schwenke, A. Pradhan, and H. Partridge, quoted in C.W. Bauschlicher and H. Partridge, J. Chem. Phys. 103 (1995) 10589.

r) Quartic force field calculated at CCSD(T)/VQZ+1 level for the purposes of this work.