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 |
TAEe [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.