Computational Chemistry

Table 5.7

Errors in HF/3–21G

(*

), HF/6–31G*, and MP2(fc)/6–31G* bond lengths and angles, from Fig.

5.23

C–H

O–H, N–H, S–H

C–C

C–O, N, F, Cl, S

Angles

MeOH

H

O 2

Me

CO 2

MeOH

H

O (HOH) 2

#

0.015/

#

0.013/

#

0.004

0.009/

#

0.010/0.011

0.008/0.007/0.006

0.020/

#

0.021/0.004

3.2/1.0/

#

0.6

#

0.009/

#

0.006/0.003

HCHO

H

O 2

2

CH

CH 3

3

HCHO

H

O 2

2

(HOO)

#

0.033/

#

0.024/

#

0.012

0.005/

#

0.016/0.011

0.011/

#

0.010/

#

0.003

#

0.001/

#

0.024/0.013

#

0.5/2.1/

#

1.4

MeF

MeOH

CH

CH 2

2

MeF

MeOH (HCO)

#

0.021/

#

0.018/

#

0.008

0.003/

#

0.017/0.007

#

0.024/

#

0.022/

#

0.002

0.021/

#

0.018/0.008

#

0.9/0.0/

#

0.9

(COH)2.3/1.4/

#

0.6

HCN

HOF

HCCH

HCN

HCHO (HCH)

#

0.015/

#

0.006/0.004

0.010/

#

0.014/0.013

#

0.015/

#

0.017/0.015

#

0.016/

#

0.020/0.024

#

1.6/

#

0.8/

#

0.9

MeNH

2

MeNH

2

CH

CH 3

CH 2

3

MeNH

2

MeF (HCH)

#

0.009/

#

0.008/0.001

#

0.007/

#

0.008/0.008

0.015/0.002/0.000

0.000/

#

0.018/

#

0.006

#

1.1/

#

0.7/

#

0.8

#

0.016/

#

0.015/

#

0.007

CH

CH 3

3

HOCl

CH

CHCH 2

3

Me

CO 2

HOF (HOF)

#

0.012/

#

0.010/

#

0.003

#

0.002/

#

0.024/0.004

0.009/0.001/

#

0.002

#

0.011/

#

0.030/0.006

2.2/3.0/0.4

#

0.002/0.000/0.020

CH

CH 2

2

H

S 2

HCCCH

3

MeCl

MeNH

2

(HCN)

#

0.011/

#

0.009/0.000

#

0.009/

#

0.010/0.004

0.007/0.009/0.004

0.025/0.004/

#

0.002

0.9/0.9/1.5

#

0.018/

#

0.019/0.014

CHCH

MeSH

MeSH

Me

CO (CCC) 2

#

0.010/

#

0.004/0.005

#

0.009/

#

0.009/0.005

0.003/

#

0.001/

#

0.003

#

2.2/

#

0.6/

#

0.7

MeCl

Me

SO 2

CH

CH 3

(HCH) 3

#

0.020/

#

0.018/

#

0.007

#

0.008/

#

0.003/0.010

0.3/

#

0.1/

#

0.1

MeSH

CH

CH 2

(HCH) 2

#

0.010/

#

0.009/0.000

#

1.6/

#

1.4/

#

1.2

#

0.011/

#

0.010/

#

0.001

CH

CH 3

CH 2

3

(CCC)

#

0.8/0.4/

#

0.1

(continued

)

5.5 Applications of the Ab initio Method 285