appendices.doc 261KB Jun 05 2011 09:30:46 PM

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Table I. Force Constants and Reference Values in the QMFF for Amides A. Bond length

E = 2_K

b (b - b0)2 + 3Kb(b - b0)3 + 4Kb(b - b0)4

b0 2Kb 3Kb 4Kb

bond (Å) (kcal mol-1_Å-2₎ _{(kcal mol}-1_Å-3₎ _{(kcal mol}-1_Å-4₎

C'-O' 1.1920

-2568.6 3155.8

C'-N 1.3983 443.4

1415.3

C'-H 1.0934

-780.5 896.3

C-N 1.4416

-676.4 650.0

H*-N 1.0015

-1300.8 1908.3

C-C' 1.5103

-522.3 490.0

H-C 1.0845

-851.3 1040.0

C-C 1.5297

-586.1 758.0

B. Bond angle E = 2_K

( - 0)2 + 3K( - 0)3 + 4K( - 0)4

0 2K 3K 4K

angle (degrees) (kcal mol -1_rad-2₎ _{(kcal mol}-1_rad-3₎ _{(kcal mol}-1_rad-4₎

N-C'-O' 124.5 115.2 -41.0 -13.3

H-C'-O' 117.8 54.7 -26.8 0.0

H-C'-N 110.4 62.1 -22.0 0.0

C-N-C' 111.0 38.0 -8.0 -8.1

C'-N-H* 117.0 44.6 -9.7 0.0

C-N-H* 113.9 54.7 -23.9 0.0

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H-C-N 108.9 68.3 3.5 0.0

C-C'-O 123.1 66.1 -20.5 0.2

C-C'-N 116.9 46.9 -13.1 -10.4

H*-N-H* 112.9 46.7 -11.3 0.0

C-C-C' 108.5 61.9 -11.3 -13.1

C'-C-H 107.7 48.3 -34.3 0.0

C-N-C 111.6 47.2 -10.2 -10.1

C'-C-N 100.6 62.0 -6.3 -12.7

N-C'-N 122.5 123.9 -43.7 -28.9

C'-N-C' 122.0 90.8 -31.3 -21.1

H-C-H 107.7 51.5 -8.9 -10.8

H-C-C 110.8 52.7 -10.9 -11.3

C. Torsion angle E = 1_K

(1 - cos) + 2K(1 - cos2) + 3K(1 - cos3)

1_K

 2K 3K

torsion (kcal mol-1₎ _{(kcal mol}-1₎ _{(kcal mol}-1₎

O'-C'-N-C 0.830 3.723 -0.050

O'-C'-N-H* -1.882 3.043 -0.373

H-C'-N-C 0.334 2.584 -0.401

H-C'-N-H* -0.008 2.619 -0.090

C-C-N-C' 0.020 -0.019 0.013

H-C-N-C' 0.031 -0.037 -0.058

C-C-N-H* -0.069 -0.011 -0.002

H-C-N-H* -0.021 -0.113 -0.175

C-C-C-N 0.108 0.080 -0.287

H-C-C-N -0.025 0.031 -0.207

C-C'-N-H* -0.915 2.385 -0.238

C-C-C'-O' 0.063 0.042 0.080

H-C-C'-O' -0.258 0.002 0.053

C-C-C'-N -0.053 0.056 -0.076

H-C-C'-N 0.241 -0.013 -0.098

C-C-C-C' 0.108 0.080 -0.287

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C-C-N-C -0.002 -0.010 0.001

H-C-N-C 0.058 0.051 -0.236

C'-C-C-C' 0.108 0.080 -0.287

C'-C-C-N 0.108 0.080 -0.287

C'-C-N-C' -0.098 0.109 -0.088

C'-C-N-H* 0.078 0.108 0.104

N-C-C'-O' 0.128 0.174 0.129

N-C-C'-N -0.127 0.180 -0.126

C-C'-N-C -0.753 2.739 0.090

C'-C-N-C -0.005 0.007 0.006

N-C'-N-H* -0.818 0.516 -1.233

O'-C'-N-C' -0.452 1.390 -0.834

H-C'-N-C' 0.212 1.246 0.047

H-C-C-H -1.152 0.012 -0.179

D. Out-of-plane E = 2_K

2

2_K



out-of-plane (kcal mol-1 _rad-2₎

H-C'-N-O' 42.126

C-N-C'-H* 1.250

C-C'-N-O' 44.242

C'-N-H*-H* 0.000

C-N-C-C' 4.247

N-C'-N-O' 49.203

C'-N-C'-H* 0.000

E. Van der Waals interaction

E =  [2(r*/r)9 _{- 3(r*/r)}6_{] where r* = [(r}

i*6 + rj*6) /2] 1/6

and  = (ij) 1/2 2 (ri*rj*)3/(ri*6 + rj*6)

ri* i

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H* 1.098 0.013

O' 3.535 0.267

C' 3.308 0.120

N 4.070 0.106

H 2.995 0.020

C 4.010 0.054

F. Bond increment

E = 332.0 qi qj / rij; where qi =



_k ik. Each ikdonates positive charge to the first atom listed

and corresponding negative charge to the second atom. ik

bond (electrons)

C'–O' 0.396

C–N 0.211

H*–N 0.440

C'–N 0.000

H–C' 0.046

C'–C 0.000

H–C 0.053

C–C 0.000

G. Bond/bond

E = Kbb'(b - b0)(b'- b'0) Kbb'

bond/bond (kcal mol-1 _Å-2₎

O'-C'/C'-N 200.718

O'-C'/C'-H 61.122

N-C'/C'-H 4.058

C'-N/N-C 17.563

C'-N/N-H* -6.250

C-N/N-H* -5.030

N-C/C-C 5.137

N-C/C-H 22.173

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C-C'/C'-N -9.389

N-H*/H*-N -0.820

C'-C/C-C 7.855

C'-C/C-H 1.031

N-C/C-N -2.171

N-C/C-C' -5.558

N-C'/C'-N 37.613

H-C/H-C 11.769

H-C/C-C 11.310

H. Bond/angle

E = Kb(b - b0)(- 0)

Kb

bond/angle (kcal mol-1_Å-1_rad-1₎

C'-O'/N-C'-O' 75.9

C'-N/N-C'-O' 90.9

C'-O'/H-C'-O' 71.1

C'-H/H-C'-O' 22.1

C'-N/H-C'-N 45.4

C'-H/H-C'-N 32.4

C'-N/C-N-C' 21.5

C-N/C-N-C' 5.5

C'-N/C'-N-H* 42.9

H*-N/C'-N-H* 15.7

C-N/C-N-H* 17.2

H*-N/C-N-H* 8.6

C-N/C-C-N 6.7

C-C/C-C-N -7.9

C-N/H-C-N 50.6

C-H/H-C-N 15.5

C'-O'/C-C'-O' 53.8

C-C'/C-C'-O' 50.7

C'-N/C-C'-N 8.8

C-C'/C-C'-N 36.8

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C-C'/C-C-C' 23.0

C-C/C-C-C' 26.3

C-C'/C'-C-H 18.1

C-H/C'-C-H 13.3

C-N/C-N-C -3.0

C-N/C'-C-N 25.2

C-C'/C'-C-N -7.5

C'-N/N-C'-N 98.7

C'-N/C'-N-C' 29.1

H-C/H-C-H 22.7

H-C/H-C-C 13.9

C-C/H-C-C 34.5

I. Angle/angle

E = K'( - 0)('- '0)

K_’

angle/angle common bond (kcal mol-1_rad-2₎

C-C-N/H-C-N C-N -1.00

C-C-H/C-C-N C-C -4.88

H-C-N/H-C-N C-N 3.71

C-C-H/H-C-N C-H -1.29

H-C-H/H-C-N C-H 6.18

C-C-C'/C'-C-H C-C' 2.96

C-C-C'/C-C-H C-C -2.64

C'-C-H/C'-C-H C-C' -5.07

C-C-H/C'-C-H C-H 1.57

C'-C-H/H-C-H C-H -4.91

C-C-N/C-C-N C-N -0.72

C-C-C/C-C-N C-C 0.22

C'-C-N/H-C-N C-N 4.39

C'-C-H/C'-C-N C-C' 0.08

C'-C-H/H-C-N C-H -2.39

C-C-C'/C'-C-N C-C' 8.24

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C-C-C'/C-C-N C-C -1.23

H-C-H/H-C-H H-C 0.93

H-C-H/H-C-C H-C 1.57

H-C-C/H-C-C H-C 3.12

H-C-C/H-C-C C-C -2.18

J. Angle/angle/torsion

E = K’( - 0)(' - '0) cos

K_'

angle/angle/torsion (kcal mol-1_rad-2₎

N-C'-O'/C-N-C'/O'-C'-N-C -22.5

N-C'-O'/C'-N-H*/O'-C'-N-H* -10.6

H-C'-N/C-N-C'/H-C'-N-C -8.1

H-C'-N/C'-N-H*/H-C'-N-H* -7.8

C-C-N/C-N-C'/C-C-N-C' -10.8

H-C-N/C-N-C'/H-C-N-C' -11.8

C-C-N/C-N-H*/C-C-N-H* -6.7

H-C-N/C-N-H*/H-C-N-H* -9.7

C-C-C/C-C-N/C-C-C-N -1.5

C-C-H/C-C-N/H-C-C-N -18.5

C-C'-N/C'-N-H*/C-C'-N-H* -1.9

C-C-C'/C-C'-O'/C-C-C'-O' -11.6

C'-C-H/C-C'-O'/H-C-C'-O' -22.2

C-C-C'/C-C'-N/C-C-C'-N -7.9

C'-C-H/C-C'-N/H-C-C'-N -17.7

C-C-C/C-C-C'/C-C-C-C' -0.6

C-C-C'/C-C-H/C'-C-C-H -7.8

C-C-N/C-N-C/C-C-N-C -2.5

H-C-N/C-N-C/H-C-N-C -17.7

C-C-C'/C-C-C'/C'-C-C-C' 0.2

C-C-C'/C-C-N/C'-C-C-N 0.5

C'-C-N/C-N-C'/C'-C-N-C' -13.4

C'-C-N/C-N-H*/C'-C-N-H* -1.4

C'-C-N/C-C'-O'/N-C-C'-O' -9.5

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C-C'-N/C-N-C'/C-C'-N-C -9.5

C'-C-N/C-N-C/C'-C-N-C 0.2

N-C'-N/C'-N-H*/N-C'-N-H* -2.2

N-C'-O'/C'-N-C'/O'-C'-N-C' -4.9

H-C'-N/C'-N-C'/H-C'-N-C' -1.1

H-C-C/H-C-C/H-C-C-H -14.8

K. Bond/torsion(Type 1)

E = (b- b0) [1Kbcos + 2Kbcos2 + 3Kbcos3

1_K

b 2Kb 3Kb

bond/torsion (kcal mol-1_Å-1₎ _{(kcal mol}-1_Å-1₎ _{(kcal mol}-1_Å-1₎

C'-N/O'-C'-N-C -12.797 20.736 -2.568

C'-N/O'-C'-N-H* -1.316 8.905 -0.703

C'-N/H-C'-N-C -16.993 4.645 -4.365

C'-N/H-C'-N-H* -1.399 7.542 -3.346

C-N/C-C-N-C' -5.725 -0.580 -0.985

C-N/H-C-N-C' -0.100 -3.282 1.678

C-N/C-C-N-H* -5.131 -4.908 0.051

C-N/H-C-N-H* -1.703 4.066 1.171

C-C/C-C-C-N -6.134 -4.786 -1.919

C-C/H-C-C-N -5.946 -0.861 -0.068

C'-N/C-C'-N-H* -0.768 6.863 -1.542

C-C'/C-C-C'-O' 0.491 -0.159 0.177

C-C'/H-C-C'-O' 0.342 1.324 1.390

C-C'/C-C-C'-N -2.907 -2.236 2.767

C-C'/H-C-C'-N 0.333 -0.601 1.160

C-C/C-C-C-C' -2.311 0.328 -1.002

C-C/C'-C-C-H -5.078 1.806 -1.103

C-N/C-C-N-C -6.822 -1.530 -4.325

C-N/H-C-N-C -3.323 0.472 1.400

C-C/C'-C-C-C' 2.139 0.848 -0.270

C-C/C'-C-C-N -1.770 -5.899 -4.924

C-N/C'-C-N-C' -6.875 -7.398 -7.869

C-N/C'-C-N-H* -2.104 5.859 -0.765

C-C'/N-C-C'-O' -6.527 7.099 0.619

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C'-N/C-C'-N-C -13.408 4.941 -4.111

C-N/C'-C-N-C 1.828 -5.164 -4.479

C'-N/N-C'-N-H* -1.803 -6.429 3.201

C'-N/O'-C'-N-C' -0.162 -1.738 0.983

C'-N/H-C'-N-C' -0.699 -0.856 -1.197

C-C/H-C-C-H -16.582 -0.784 -0.901

L. Bond/torsion(type 2)

E =(b'- b'0) [1Kb' cos + 2Kb'cos2 + 3Kb'cos3

1_K

b' 2Kb' 3Kb'

bond/torsion (kcal mol-1_Å-1₎ _{(kcal mol}-1_Å-1₎ _{(kcal mol}-1_Å-1₎

C'-O'/O'-C'-N-C 0.178 -3.091 0.809

C-N/O'-C'-N-C 0.232 1.051 -0.146

C'-O'/O'-C'-N-H* -1.102 -3.831 1.807

H*-N/O'-C'-N-H 0.176 0.281 0.118

C'-H/H-C'-N-C -0.859 -0.007 0.215

C-N/H-C'-N-C -0.773 0.830 -0.094

C'-H/H-C'-N-H* -0.372 0.693 0.517

H*-N/H-C'-N-H* 0.143 0.808 0.170

C'-N/C-C-N-C' -0.180 -1.358 1.128

C-C/C-C-N-C' -0.295 0.005 0.081

C'-N/H-C-N-C' 0.332 1.700 -0.084

C-H/H-C-N-C' -0.531 1.188 0.194

H*-N/C-C-N-H* -0.144 -0.105 -0.600

C-C/C-C-N-H* 0.191 0.002 0.192

H*-N/H-C-N-H* -0.709 0.238 0.450

C-H/H-C-N-H* -1.302 0.410 0.128

C-N/C-C-C-N -0.115 -0.059 0.037

C-C/C-C-C-N 0.108 0.015 0.075

C-N/H-C-C-N 0.438 0.364 0.673

C-H/H-C-C-N -0.087 -0.545 -0.272

C-C'/C-C'-N-H* -1.011 0.814 0.610

H*-N/C-C'-N-H* 0.929 0.243 0.209

C'-O'/C-C-C'-O' -0.407 0.118 -0.221

C-C/C-C-C'-O' 0.385 0.073 0.152

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C-H/H-C-C'-O' 1.760 0.410 0.568

C'-N/C-C-C'-N -0.399 -0.443 -0.256

C-C/C-C-C'-N -0.381 -0.011 -0.166

C'-N/H-C-C'-N 0.515 -0.389 0.845

C-H/H-C-C'-N -0.039 1.136 0.005

C-C'/C-C-C-C' 0.008 0.009 -0.001

C-C/C-C-C-C' 0.009 0.000 0.005

C-C'/C'-C-C-H -0.030 0.526 -0.642

C-H/C'-C-C-H -0.014 -0.046 -0.109

C-N/C-C-N-C -0.119 -0.011 -0.135

C-C/C-C-N-C -0.181 -0.164 -0.112

C-N/H-C-N-C 0.181 0.470 -0.108

C-H/H-C-N-C -1.954 1.159 0.979

C-C'/C'-C-C-C' 0.008 -0.001 -0.006

C-N/C'-C-C-N -0.244 -0.214 -0.214

C-C'/C'-C-C-N -0.191 -0.161 -0.168

C'-N/C'-C-N-C' -0.645 0.617 -0.631

C-C'/C'-C-N-C' -0.259 0.311 -0.406

H*-N/C'-C-N-H* 1.305 0.430 0.085

C-C'/C'-C-N-H* 0.158 0.487 0.134

C-N/N-C-C'-O' -0.110 0.379 0.234

C'-O'/N-C-C'-O' 1.456 -0.479 0.945

C-N/N-C-C'-N -0.252 0.104 -0.865

C'-N/N-C-C'-N -0.018 0.028 -1.389

C-C'/C-C'-N-C 0.135 -0.671 0.418

C-N/C-C'-N-C 0.333 -0.165 -0.206

C-N/C'-C-N-C 0.026 -0.131 -0.117

C-C'/C'-C-N-C 0.097 -0.115 -0.134

H*-N/N-C'-N-H* -0.707 -1.033 0.191

C'-N/N-C'-N-H* 0.112 -0.767 -0.006

C'-O'/O'-C'-N-C' -1.017 1.204 -0.996

C'-N/O'-C'-N-C' 0.250 -0.699 0.386

C'-N/H-C'-N-C' -0.306 -0.609 -0.330

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M. Angle/torsion

E = (- 0) [1Kcos + 2Kcos2 + 3Kcos3 1_K

 2K 3K

angle/torsion (kcal mol-1_rad-1₎ _{(kcal mol}-1_rad-1₎ _{(kcal mol}-1_rad-1₎

N-C'-O'/O'-C'-N-C 6.444 5.843 2.482

C-N-C'/O'-C'-N-C 10.787 3.117 -0.320

N-C'-O'/O'-C'-N-H* -3.803 0.523 0.793

C'-N-H*/O'-C'-N-H* 6.115 1.803 0.359

H-C'-N/H-C'-N-C 0.197 4.539 0.310

C-N-C'/H-C'-N-C 8.960 -0.511 -0.311

H-C'-N/H-C'-N-H* -3.163 2.963 -0.211

C'-N-H*/H-C'-N-H* 5.694 1.463 -0.046

C-N-C'/C-C-N-C' -2.207 1.637 1.039

C-C-N/C-C-N-C' -1.095 0.082 1.765

C-N-C'/H-C-N-C' 0.054 -0.495 -0.112

H-C-N/H-C-N-C' -2.197 3.012 0.777

C-N-H*/C-C-N-H* -1.489 0.523 -0.355

C-C-N/C-C-N-H* -4.198 3.925 -0.054

C-N-H*/H-C-N-H* -0.992 0.523 0.114

H-C-N/H-C-N-H* -5.365 2.011 0.347

C-C-N/C-C-C-N 0.295 0.232 -1.152

C-C-C/C-C-C-N -0.797 -2.461 0.360

C-C-N/H-C-C-N -2.872 0.337 -0.569

C-C-H/H-C-C-N -1.807 2.454 -1.751

C-C'-N/C-C'-N-H* -3.208 1.871 1.410

C'-N-H*/C-C'-N-H* 4.950 0.540 0.143

C-C'-O'/C-C-C'-O' 0.978 0.864 0.975

C-C-C'/C-C-C'-O' 0.128 -1.986 -0.790

C-C'-O'/H-C-C'-O' -2.166 1.059 -0.302

C'-C-H/H-C-C'-O' 13.232 -0.703 0.519

C-C'-N/C-C-C'-N 3.076 0.729 -0.111

C-C-C'/C-C-C'-N 3.160 -0.049 -2.002

C-C'-N/H-C-C'-N 2.900 0.735 1.218

C'-C-H/H-C-C'-N 10.283 0.011 1.001

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C-C-C/C-C-C-C' -0.378 0.464 -0.331

C-C-C'/C'-C-C-H -1.082 -1.369 -0.916

C-C-H/C'-C-C-H 0.023 2.060 -2.042

C-N-C/C-C-N-C 1.874 2.990 -0.223

C-C-N/C-C-N-C -0.417 2.571 0.397

C-N-C/H-C-N-C 0.513 -0.577 -0.283

H-C-N/H-C-N-C -2.541 1.884 0.733

C-C-C'/C'-C-C-C' 5.002 1.813 -0.065

C-C-N/C'-C-C-N -2.292 -1.202 -2.330

C-C-C'/C'-C-C-N -1.959 -3.449 -0.383

C-N-C'/C'-C-N-C' -3.491 1.270 -1.604

C'-C-N/C'-C-N-C' 6.929 2.668 1.883

C-N-H*/C'-C-N-H* 0.159 -0.812 -3.753

C'-C-N/C'-C-N-H* -5.324 2.945 0.548

C'-C-N/N-C-C'-O' -2.636 -4.079 3.410

C-C'-O'/N-C-C'-O' 1.425 5.477 7.985

C'-C-N/N-C-C'-N -1.188 -1.194 3.564

C-C'-N/N-C-C'-N -0.065 0.924 -9.223

C-C'-N/C-C'-N-C 6.106 4.247 4.769

C-N-C'/C-C'-N-C 8.574 2.588 0.587

C-N-C/C'-C-N-C -0.650 3.641 3.724

C'-C-N/C'-C-N-C 5.071 -5.186 -3.202

C'-N-H*/N-C'-N-H* 1.178 -1.183 0.899

N-C'-N/N-C'-N-H* -3.877 2.284 0.106

N-C'-O'/O'-C'-N-C' -2.282 3.478 -0.413

C'-N-C'/O'-C'-N-C' -0.440 -0.079 -0.462

H-C'-N/H-C'-N-C' -3.737 3.603 1.457

C'-N-C'/H-C'-N-C' 2.356 -1.832 0.859

H-C-C/H-C-C-H -1.622 0.739 -0.449

Table II.A. Comparison of Formamide Structures Optimizedby Ab Initio

Calculation (HF/6-31G*) and by the HDFF and QMFF Force Fields.

Structures

(13)

Bonds (Å)

C'1 - O'2 1.193 1.187 (-0.006) 1.193 (0.000)

C'1 - N3 1.348 1.377 (0.029) 1.347 (-0.001)

C'1 - H6 1.091 1.095 (0.004) 1.089 (-0.002)

N3 - H*4 0.996 0.999 (0.003) 0.995 (-0.001)

N3 - H*5 0.993 0.998 (0.005) 0.992 (-0.001)

Angles (degrees)

O'2 - C'1 - N3 124.9 123.2 (-1.8) 124.2 (-0.7)

O'2 - C'1 - H6 122.3 120.4 (-1.9) 122.2 (-0.2)

N3 - C'1 - H6 112.7 116.4 (3.7) 113.6 (0.9)

C'1 - N3 -H*4 119.3 118.8 (-0.5) 116.8 (-2.4)

C'1 - N3 -H*5 121.8 123.0 (1.2) 123.4 (1.5)

H*4 - N3 -H*5 118.9 118.2 (-0.7) 119.8 (0.9)

Torsions (degrees)

O'2 - C'1 - N3 - H*4 0.0 0.0 (0.0) 0.0 (0.0)

O'2 - C'1 - N3 - H*5 180.0 180.0 (0.0) 180.0 (0.0)

H6 - C'1 - N3 - H*4 180.0 180.0 (0.0) 180.0 (0.0)

H6 - C'1 - N3 - H*5 0.0 0.0 (0.0) 0.0 (0.0)

Out-of-Planes (degrees)

O'2 - C'1 - N3 - H6 0.0 0.0 (0.0) 0.0 (0.0)

C'1 - N3 - H*4 - H*5 0.0 0.0 (0.0) 0.0 (0.0)

Table II.B. Comparison of Planar Acetamide Structures Optimizedby Ab Initio

Structures

Coordinate HF/6-31G* HDFF QMFF

Bonds (Å)

O'1 - C'2 1.198 1.187 (-0.011) 1.196 (-0.002)

C'2 - N3 1.356 1.369 (0.013) 1.352 (-0.004)

C'2 - C4 1.514 1.509 (-0.005) 1.503 (-0.011)

N3 - H*5 0.995 0.998 (0.003) 0.995 (0.000)

N3 - H*6 0.993 0.996 (0.003) 0.990 (-0.002)

C4 - H7 1.085 1.085 (0.000) 1.084 (-0.001)

C4 - H8 1.085 1.085 (0.000) 1.084 (-0.001)

C4 - H9 1.080 1.085 (0.005) 1.079 (-0.001)

(14)

O'1 - C'2 - N3 122.2 121.3 (-0.9) 121.4 (-0.8)

O'1 - C'2 - C4 122.9 123.4 (0.5) 123.0 (0.1)

N3 - C'2 - C4 114.9 115.3 (0.4) 115.7 (0.7)

C'2 - N3 -H*5 118.5 118.8 (0.3) 116.5 (-2.1)

C'2 - N3 -H*6 122.7 122.6 (-0.1) 123.5 (0.8)

H*5 - N3 -H*6 118.7 118.6 (-0.1) 120.1 (1.3)

C'2 - C4 - H7 110.6 109.4 (-1.2) 110.7 (0.1)

C'2 - C4 - H8 110.6 109.4 (-1.2) 110.7 (0.1)

C'2 - C4 - H9 108.9 111.2 (2.3) 109.3 (0.4)

H7 - C4 - H8 108.0 106.9 (-1.1) 108.9 (0.9)

H7 - C4 - H9 109.4 109.9 (0.5) 108.6 (-0.8)

H8 - C4 - H9 109.4 109.9 (0.5) 108.6 (-0.8)

Torsions (degrees)

O'1 - C'2 - N3 - H*5 0.0 0.0 (0.0) 0.0 (0.0)

O'1 - C'2 - N3 - H*6 180.0 180.0 (0.0) 180.0 (0.0)

C4 - C'2 - N3 - H*5 180.0 180.0 (0.0) 180.0 (0.0)

C4 - C'2 - N3 - H*6 0.0 0.0 (0.0) 0.0 (0.0)

O'1 - C'2 - C4 - H7 120.2 121.6 (1.4) 119.6 (-0.6)

O'1 - C'2 - C4 - H8 239.8 238.4 (-1.4) 240.4 (0.6)

O'1 - C'2 - C4 - H9 0.0 0.0 (0.0) 0.0 (0.0)

N3 - C'2 - C4 - H7 300.2 301.6 (1.4) 299.6 (-0.6)

N3 - C'2 - C4 - H8 59.8 58.4 (-1.4) 60.4 (0.6)

N3 - C'2 - C4 - H9 180.0 180.0 (0.0) 180.0 (0.0)

O'1 - C'2 - C4 - N3 0.0 0.0 (0.0) 0.0 (0.0)

C'2 - N3 - H*6 - H*5 0.0 0.0 (0.0) 0.0 (0.0)

Appendix II.C. Comparison of Planar N-Methylformamide Trans and Cis Structures Optimized by Ab Initio Calculation (HF/6-31G*) and by the HDFF and QMFF Force Fields.

trans cis

Coordinate HF/6-31G* HDFF QMFF HF/6-31G* HDFF QMFF

Bonds (Å)

O'1 -C'2 1.196 1.190 (-0.006) 1.196 (0.001) 1.195 1.189 (-0.006) 1.194 (-0.001)

C'2 -N3 1.345 1.401 (0.056) 1.348 (0.003) 1.347 1.389 (0.041) 1.349 (0.002)

C'2 -H5 1.091 1.094 (0.003) 1.088 (-0.003) 1.091 1.095 (0.004) 1.092 (0.000)

N3 - C4 1.448 1.452 (0.004) 1.445 (-0.003) 1.442 1.450 (0.007) 1.440 (-0.002)

N3 -H*6 0.993 0.999 (0.006) 0.995 (0.002) 0.997 1.001 (0.004) 1.000 (0.003)

C4 -H7 1.081 1.085 (0.004) 1.083 (0.002) 1.082 1.086 (0.003) 1.082 (0.000)

C4 -H8 1.083 1.086 (0.003) 1.085 (0.002) 1.084 1.086 (0.001) 1.085 (0.001)

C4 -H9 1.083 1.086 (0.003) 1.085 (0.002) 1.084 1.086 (0.001) 1.085 (0.001)

Angles (degrees)

(15)

O'1 -C'2 -H5 122.2 119.6 (-2.7) 121.8 (-0.4) 122.1 120.0 (-2.2) 121.9 (-0.2)

N3 -C'2 -H5 113.0 114.6 (1.6) 113.6 (0.6) 112.9 116.6 (3.7) 113.0 (0.0)

C'2 -N3 - C4 121.8 122.5 (0.7) 120.8 (-0.9) 125.4 124.5 (-0.9) 124.5 (-0.9)

C'2 -N3 -H*6 118.7 120.0 (1.3) 120.7 (2.0) 115.5 117.1 (1.6) 115.4 (-0.1)

C4 -N3 -H*6 119.6 117.5 (-2.0) 118.5 (-1.1) 119.1 118.4 (-0.7) 120.1 (1.0)

N3 - C4 -H7 108.7 110.2 (1.5) 109.0 (0.3) 109.3 110.7 (1.5) 108.3 (-1.0)

N3 - C4 -H8 110.9 110.7 (-0.2) 111.1 (0.2) 111.4 110.5 (-0.8) 111.4 (0.0)

N3 - C4 -H9 110.9 110.7 (-0.2) 111.1 (0.2) 111.3 110.5 (-0.8) 111.4 (0.1)

H7 - C4 -H8 109.0 107.9 (-1.1) 108.4 (-0.5) 108.1 107.9 (-0.2) 108.5 (0.4)

H7 - C4 -H9 109.0 107.9 (-1.1) 108.4 (-0.5) 108.1 107.9 (-0.1) 108.5 (0.4)

H8 - C4 -H9 108.4 109.3 (1.0) 108.7 (0.3) 108.7 109.1 (0.5) 108.7 (0.0)

Torsions (degrees)

O'1 -C'2 -N3 - C4 0.0 0.0 (0.0) 0.0 (0.0) 180.1 180.0 (-0.1) 180.0 (-0.1)

O'1 -C'2 -N3 -H*6 180.0 180.0 (0.0) 180.0 (0.0) 359.9 0.0 (0.1) 0.0 (0.1)

H5 -C'2 -N3 - C4 180.0 180.0 (0.0) 180.0 (0.0) 0.1 0.0 (-0.1) 0.0 (-0.1)

H5 -C'2 -N3 -H*6 0.0 0.0 (0.0) 0.0 (0.0) 179.9 180.0 (0.1) 180.0 (0.1)

C'2 -N3 - C4 -H7 180.0 180.0 (0.0) 180.0 (0.0) 359.7 0.0 (0.3) 0.0 (0.3)

C'2 -N3 - C4 -H8 299.8 299.3 (-0.5) 299.4 (-0.3) 119.0 119.5 (0.6) 119.2 (0.3)

C'2 -N3 - C4 -H9 60.2 60.7 (0.5) 60.6 (0.3) 240.4 240.5 (0.1) 240.8 (0.4)

H*6 -N3 - C4 -H7 0.0 0.0 (0.0) 0.0 (0.0) 179.9 180.0 (0.1) 180.0 (0.1)

H*6 -N3 - C4 -H8 119.8 119.3 (-0.5) 119.4 (-0.3) 299.2 299.5 (0.4) 299.2 (0.1)

H*6 -N3 - C4 -H9 240.2 240.7 (0.5) 240.6 (0.3) 60.6 60.5 (-0.2) 60.8 (0.1)

Out-of-Planes (degrees) O’

'1-C'2 -N3 -H5 0.0

(0.0)0.0(0.0)0.00.0 (0.0 0.0(0.0)

C'2 -N3 -H*6 - C4 0.0 (0.0)0.0(0.0)0.00.0 (0.0 0.0(0.0)

Appendix II.D. Comparison of Planar N-Methylacetamide Trans and Cis Structures Optimized by Ab Initio Calculation (HF/6-31G*) and by the HDFF and QMFF Force Fields.

trans cis

Coordinate HF/6-31G* HDFF QMFF HF/6-31G* HDFF QMFF

Bonds (Å)

(16)

Angles (degrees)

C'2 - C1- H7 108.6 108.8 (0.2) 107.8 (-0.8) 111.1 109.4 (-1.7) 111.0 (-0.1) C'2 - C1- H8 113.7 112.8 (-0.9) 114.4 (0.7) 108.3 111.4 (3.1) 108.9 (0.6) C'2 - C1- H9 108.6 108.8 (0.2) 107.8 (-0.8) 111.1 109.4 (-1.7) 111.0 (-0.1) H7 - C1- H8 109.1 109.3 (0.2) 108.9 (-0.2) 109.3 109.8 (0.5) 108.3 (-1.0) H7 - C1- H9 107.6 107.7 (0.1) 108.9 (1.3) 107.8 106.9 (-0.9) 109.2 (1.4) H8 - C1- H9 109.1 109.3 (0.2) 108.9 (-0.2) 109.3 109.8 (0.5) 108.3 (-1.0) C1 - C'2- N3 116.3 114.5 (-1.8) 117.8 (1.5) 116.6 118.7 (2.1) 115.6 (-1.0) C1 - C'2- O'5 121.5 121.9 (0.4) 120.1 (-1.4) 122.0 121.3 (-0.7) 122.5 (0.5) N3 - C'2- O'5 122.2 123.7 (1.5) 122.1 (-0.1) 121.3 120.0 (-1.3) 121.9 (0.6) C'2 - N3- C4 121.4 123.2 (1.8) 120.2 (-1.2) 127.4 126.5 (-0.9) 126.2 (-1.2) C'2 - N3- H*6 119.6 119.2 (-0.4) 120.9 (1.3) 114.0 115.5 (1.5) 114.6 (0.7) C4 - N3- H*6 119.1 117.6 (-1.5) 118.9 (-0.2) 118.6 117.9 (-0.7) 119.2 (0.6) N3 - C4- H10 111.0 110.7 (-0.3) 111.1 (0.1) 112.2 110.9 (-1.3) 111.5 (-0.7) N3 - C4- H11 108.6 110.2 (1.6) 109.0 (0.4) 108.2 109.9 (1.7) 108.3 (0.1) N3 - C4- H12 111.0 110.7 (-0.3) 111.1 (0.1) 112.2 110.9 (-1.3) 111.5 (-0.7) H10- C4- H11 109.0 107.9 (-1.1) 108.4 (-0.6) 107.8 107.7 (-0.1) 108.2 (0.4) H10- C4- H12 108.3 109.3 (1.0) 108.8 (0.5) 108.5 109.6 (1.1) 109.0 (0.5) H11 - C4- H12 109.0 107.9 (-1.1) 108.4 (-0.6) 107.8 107.7 (-0.1) 108.2 (0.4)

Torsions (degrees)

H7- C1- C'2 - N3 238.4 238.5 (0.1) 238.7 (0.3) 300.0 301.6 (1.6) 299.2 H7- C1- C'2 - O'5 58.4 58.5 (0.1) 58.7 (0.3) 120.0 121.6 (1.6) 119.2(-0.8) H8- C1- C'2 - N3 0.0 0.0 (0.0) 0.0 (0.0) 180.0 180.0 (0.0) 180.0 H8- C1- C'2 - O'5 180.0 180.0 (0.0) 180.0 (0.0) 0.0 0.0 (0.0) 0.0 (0.0) H9- C1- C'2 - N3 121.6 121.5 (-0.1) 121.3 (-0.3) 60.0 58.4 (-1.6) 60.8 (0.8) H9- C1- C'2 - O'5 301.6 301.5 (-0.1) 301.3 (-0.3) 240.0 238.4 (-1.6) 240.8 C1- C'2- N3 - C4 180.0 180.0 (0.0) 180.0 (0.0) 0.0 0.0 (0.0) 0.0 (0.0) C1- C' - N3 - H*6 0.0 0.0 (0.0) 0.0 (0.0) 180.0 180.0 (0.0) 180.0 O'5- C'2 - N3- C4 0.0 0.0 (0.0) 0.0 (0.0) 180.0 180.0 (0.0) 180.0 O'5- C'2 - N3- H*6 180.0 180.0 (0.0) 180.0 (0.0) 0.0 0.0 (0.0) 0.0 (0.0) C'2- N3- C4 - H10 299.8 299.3 (-0.5) 299.4 (-0.4) 298.8 299.0 (0.2) 290.0 C'2- N3- C4 - H11 180.0 180.0 (0.0) 180.0 (0.0) 180.0 180.0 (0.0) 180.0 C'2- N3- C4 - H12 60.2 60.7 (0.5) 60.6 (0.4) 61.2 61.0 (-0.2) 61.0 (0.2) H*6 - N3- C4- H11 0.0 0.0 (0.0) 0.0 (0.0) 0.0 0.0 (0.0) 0.0 ( 0.0) H*6 - N3- C4- H12 240.2 240.7 (0.5) 240.6 (0.4) 241.2 241.0 (-0.2) 241.0

Out-of-Planes

C1 - C'2- N3- O'5 0.0 0.0 (0.0) 0.0 (0.0) 0.0 0.0 (0.0) 0.0 (0.0) C'2- N3- H*6-C4 0.0 0.0 (0.0) 0.0 (0.0) 0.0 0.0 (0.0) 0.0 (0.0) ______________________________________________________________________________________________________________

Table II.E. Comparison of N,N-Dimethylformamide Structures Optimizedby Ab Initio

Structures

(17)

O'1 - C'2 1.196 1.192 (-0.004) 1.197 (0.001)

C'2 - N3 1.349 1.415 (0.067) 1.350

(0.002)

C'2 - H6 1.091 1.094 (0.004) 1.091

(0.001)

N3 - C4 1.442 1.454 (0.012) 1.447

(0.005)

N3 - C5 1.446 1.457 (0.011) 1.448

(0.002)

C4 - H7 1.082 1.085 (0.003) 1.080

(-0.002)

C4 - H8 1.086 1.086 (0.000) 1.087

(0.001)

C4 - H9 1.086 1.086 (0.000) 1.087

(0.001)

C5 - H10 1.077 1.085 (0.008) 1.080

(0.003)

C5 - H11 1.086 1.085 (-0.001) 1.087

(0.001)

C5 - H12 1.086 1.085 (-0.001) 1.087

(0.001)

Angles (degrees)

O'1 - C'2 - N3 125.9 126.1 (0.2) 126.2 (0.3)

O'1 - C'2 - H6 121.5 118.8 (-2.7) 120.9 (-0.6)

N3 - C'2 - H6 112.6 115.0 (2.5) 112.9 (0.3)

C'2 - N3 - C4 122.0 121.3 (-0.7) 121.4 (-0.6)

C'2 - N3 - C5 120.6 122.9 (2.3) 122.1 (1.5)

C4 - N3 - C5 117.4 115.8 (-1.6) 116.6 (-0.9)

N3 - C4 - H7 110.2 111.4 (1.3) 109.3 (-0.9)

N3 - C4 - H8 110.9 110.4 (-0.5) 111.1 (0.2)

N3 - C4 - H9 110.9 110.4 (-0.5) 111.1 (0.2)

H7 - C4 - H8 108.3 108.4 (0.1) 108.3 (0.1)

H7 - C4 - H9 108.3 108.4 (0.1) 108.3 (0.1)

H8 - C4 - H9 108.2 107.6 (-0.6) 108.6 (0.3)

N3 - C5 - H10 109.0 111.7 (2.8) 109.9 (0.9)

N3 - C5 - H11 110.5 110.4 (-0.1) 111.0 (0.6)

N3 - C5 - H12 110.5 110.4 (-0.1) 111.0 (0.6)

H10 - C5 - H11 109.3 108.3 (-1.0) 108.1 (-1.1)

H10 - C5 - H12 109.3 108.3 (-1.0) 108.1 (-1.1)

H11 - C5 - H12 108.4 107.7 (-0.7) 108.5 (0.1)

Torsions (degrees)

O'1 - C'2 - N3 - C4 180.0 180.0 (0.0) 180.0 (0.0)

O'1 - C'2 - N3 - C5 0.0 0.0 (0.0) 0.0 (0.0)

H6 - C'2 - N3 - C4 0.0 0.0 (0.0) 0.0 (0.0)

(18)

C'2 - N3 - C4 - H7 0.0 0.0 (0.0) 0.0 (0.0)

C'2 - N3 - C4 - H8 240.1 239.4 (-0.7) 240.5 (0.4)

C'2 - N3 - C4 - H9 119.9 120.6 (0.7) 119.5 (-0.4)

C5 - N3 - C4 - H7 180.0 180.0 (0.0) 180.0 (0.0)

C5 - N3 - C4 - H8 60.1 59.4 (-0.7) 60.5 (0.4)

C5 - N3 - C4 - H9 299.9 300.6 (0.7) 299.5 (-0.4)

C'2 - N3 - C5 - H10 0.0 0.0 (0.0) 0.0 (0.0)

C'2 - N3 - C5 - H11 120.0 120.5 (0.5) 119.6 (-0.5)

C'2 - N3 - C5 - H12 240.0 239.5 (-0.5) 240.4 (0.5)

C4 - N3 - C5 - H10 180.0 180.0 (0.0) 180.0 (0.0)

C4 - N3 - C5 - H11 300.0 300.5 (0.5) 299.6 (-0.5)

C4 - N3 - C5 - H12 60.0 59.5 (-0.5) 60.4 (0.5)

O'1 - C'2 - N3 - H6 0.0 0.0 (0.0) 0.0 (0.0)

C'2 - N3 - C4 - C5 0.0 0.0 (0.0) 0.0 (0.0)

Table II.F. Comparison of Planar N,N-Dimethylacetamide Structures Optimized by Ab Initio

Structures

Bonds (Å)

C1 - C'2 1.518 1.520 (0.002) 1.521 (0.004)

C1 - H7 1.079 1.085 (0.006) 1.080 (0.001)

C1 - H8 1.085 1.084 (0.000) 1.084 (-0.001)

C1 - H9 1.085 1.084 (0.000) 1.084 (-0.001)

C'2 - O'3 1.203 1.192 (-0.010) 1.201 (-0.001)

C'2 - N4 1.361 1.430 (0.069) 1.366 (0.006)

N4 - C5 1.449 1.461 (0.012) 1.455 (0.006)

N4 - C6 1.445 1.459 (0.014) 1.450 (0.005)

C5 - H10 1.076 1.085 (0.009) 1.079 (0.004)

C5 - H11 1.087 1.085 (-0.001) 1.087 (0.001)

C5 - H12 1.087 1.085 (-0.001) 1.087 (0.001)

C6 - H13 1.077 1.083 (0.006) 1.078 (0.001)

C6 - H14 1.087 1.086 (-0.001) 1.088 (0.001)

C6 - H15 1.087 1.086 (-0.001) 1.088 (0.001)

Angles (degrees)

C'2 - C1 - H7 107.2 111.4 (4.2) 108.1 (0.9)

C'2 - C1 - H8 111.6 109.5 (-2.1) 111.4 (-0.3)

(19)

H7 - C1 - H8 109.1 109.5 (0.5) 108.3 (-0.8)

H7 - C1 - H9 109.1 109.5 (0.5) 108.3 (-0.8)

H8 - C1 - H9 108.1 107.3 (-0.9) 109.3 (1.1)

C1 - C'2 - O'3 119.9 119.0 (-0.9) 119.0 (-0.8)

C1 - C'2 - N4 118.0 118.3 (0.3) 118.8 (0.8)

O'3 - C'2 - N4 122.1 122.1 (0.6) 122.2 (0.1)

C'2 - N4 - C5 119.5 121.4 (1.8) 120.9 (1.4)

C'2 - N4 - C6 125.6 124.8 (-0.8) 124.9 (-0.7)

C5 - N4 - C6 114.9 113.9 (-1.0) 114.2 (-0.6)

N4 - C5 - H10 109.5 112.4 (3.0) 110.8 (1.4)

N4 - C5 - H11 110.3 110.3 (0.0) 110.8 (0.4)

N4 - C5 - H12 110.3 110.3 (0.0) 110.8 (0.4)

H10 - C5 - H11 109.3 108.0 (-1.2) 107.9 (-1.3)

H10 - C5 - H12 109.3 108.0 (-1.2) 107.9 (-1.3)

H11 - C5 - H12 108.2 107.5 (-0.6) 108.5 (0.3)

N4 - C6 - H13 111.8 113.0 (1.1) 111.1 (-0.7)

N4 - C6 - H14 110.4 110.2 (-0.2) 110.6 (0.3)

N4 - C6 - H15 110.4 110.2 (-0.2) 110.6 (0.3)

H13 - C6 - H14 108.1 108.0 (-0.1) 108.0 (-0.1)

H13 - C6 - H15 108.1 108.0 (-0.1) 108.0 (-0.1)

H14 - C6 - H15 107.9 107.4 (-0.6) 108.4 (0.5)

Torsions (degrees)

H7 - C1 - C'2 - O'3 0.0 0.0 (0.0) 0.0 (0.0)

H7 - C1 - C'2 - N4 180.0 180.0 (0.0) 180.0 (0.0)

H8 - C1 - C'2 - O'3 119.4 121.3 (1.9) 118.9 (-0.6)

H8 - C1 - C'2 - N4 299.4 301.3 (1.9) 298.9 (-0.6)

H9 - C1 - C'2 - O'3 240.6 238.7 (-1.9) 241.1 (0.6)

H9 - C1 - C'2 - N4 60.6 58.7 (-1.9) 61.1 (0.6)

C1 - C'2 - N4 - C5 180.0 180.0 (0.0) 180.0 (0.0)

C1 - C'2 - N4 - C6 0.0 0.0 (0.0) 0.0 (0.0)

O'3 - C'2 - N4 - C5 0.0 0.0 (0.0) 0.0 (0.0)

O'3 - C'2 - N4 - C6 180.0 180.0 (0.0) 180.0 (0.0)

C'2 - N4 - C5 - H10 0.0 0.0 (0.0) 0.0 (0.0)

C'2 - N4 - C5 - H11 120.3 120.7 (0.4) 119.8 (-0.5)

C'2 - N4 - C5 - H12 239.7 239.3 (-0.4) 240.2 (0.5)

C6 - N4 - C5 - H10 180.0 180.0 (0.0) 180.0 (0.0)

C6 - N4 - C5 - H11 300.3 300.7 (0.4) 299.8 (-0.5)

C6 - N4 - C5 - H12 59.7 59.3 (-0.4) 60.2 (0.5)

C'2 - N4 - C6 - H13 0.0 0.0 (0.0) 0.0 (0.0)

C'2 - N4 - C6 - H14 120.4 120.9 (0.5) 119.9 (-0.5)

C'2 - N4 - C6 - H15 239.6 239.1 (-0.5) 240.1 (0.5)

C5 - N4 - C6 - H13 180.0 180.0 (0.0) 180.0 (0.0)

C5 - N4 - C6 - H14 300.4 300.9 (0.5) 299.9 (-0.5)

C5 - N4 - C6 - H15 59.6 59.1 (-0.5) 60.1 (0.5)

(20)

C'2 - N4 - C5 - C6 0.0 0.0 (0.0) 0.0 (0.0)

Table II.G. Comparison of Urea Structures Optimized by Ab Initio Calculation (HF/6-31G*) and by the HDFF and QMFF Force Fields.

Structures

Bonds (Å)

N1 - C'2 1.373 1.308 (-0.065) 1.372 (-0.001)

N1 - H*5 0.996 0.996 (0.000) 0.996 (0.000)

N1 - H*6 0.996 0.994 (-0.003) 0.993 (-0.003)

C'2 - O'3 1.197 1.180 (-0.017) 1.192 (-0.005)

C'2 - N4 1.373 1.308 (-0.065) 1.372 (-0.001)

N4 - H*7 0.996 0.996 (0.000) 0.996 (0.000)

N4 - H*8 0.996 0.994 (-0.003) 0.993 (-0.003)

Angles (degrees)

C'2 - N1 - H*5 113.4 112.3 (-1.0) 109.3 (-4.1)

C'2 - N1 - H*6 117.7 114.5 (-3.3) 117.3 (-0.4)

H*5 - N1 - H*6 114.4 116.2 (1.7) 116.2 (1.8)

N1 - C'2 - O'3 123.0 122.5 (-0.5) 121.9 (-1.1)

N1 - C'2 - N4 114.0 115.0 (1.1) 116.2 (2.2)

O'3 - C'2 - N4 123.0 122.5 (-0.5) 121.9 (-1.1)

C'2 - N4 - H*7 113.4 112.3 (-1.0) 109.3 (-4.1)

C'2 - N4 - H*8 117.7 114.5 (-3.3) 117.3 (-0.4)

H*7 - N4 - H*8 114.4 116.2 (1.7) 116.2 (1.8)

Torsions (degrees)

H*5 - N1 - C'2 - O'3 12.6 13.9 (1.3) 9.2 (-3.4)

H*5 - N1 - C'2 - N4 192.6 193.9 (1.3) 189.2 (-3.4)

H*6 - N1 - C'2 - O'3 150.0 149.2 (-0.8) 144.2 (-5.8)

H*6 - N1 - C'2 - N4 330.0 329.2 (-0.8) 324.2 (-5.8)

N1 - C'2 - N4 - H*7 192.6 193.9 (1.3) 189.2 (-3.4)

N1 - C'2 - N4 - H*8 330.0 329.2 (-0.8) 324.2 (-5.8)

O'3 - C'2 - N4 - H*7 12.6 13.9 (1.3) 9.2 (-3.4)

O'3 - C'2 - N4 - H*8 150.0 149.2 (-0.8) 144.2 (-5.8)

Out-of Planes (degrees)

C'2 - N1 - H*6 - H*5 -37.4 -40.6 (-3.2) -40.8 (-3.3)

N1 - C'2 - O'3 - N4 0.0 0.0 (0.0) 0.0 (0.0)

(21)

Table II.H. Comparison of N-Formylformamide Structures Optimizedby Ab Initio Calculation (HF/6-31G*) and by the HDFF and QMFF Force Fields.

Structures

Bonds (Å)

O'1 - C'2 1.185 1.188 (0.003) 1.189

C'2 - N3 1.373 1.379 (0.006) 1.373

C'2 - H6 1.088 1.095 (0.007) 1.089

N3 - C'4 1.373 1.379 (0.006) 1.373

N3 - H*8 1.000 0.996 (-0.004) 0.994

C'4 - O'5 1.185 1.188 (0.003) 1.189

C'4 - H7 1.088 1.095 (0.007) 1.089

Angles (degrees)

O'1 - C'2-N3 123.7 123.6 (-0.1) 124.2 (0.5)

O'1 - C'2-H6 122.9 120.2 (-2.7) 122.9 (0.0)

N3 - C'2-H6 113.3 116.2 (2.9) 112.9 (-0.4)

C'2 - N3 - C'4 125.0 125.7 (0.7) 125.4 (0.4)

C'2 - N3 - H*8 117.5 117.2 (-0.3) 117.3 (-0.2)

C'4 - N3 - H*8 117.5 117.2 (-0.3) 117.3 (-0.2)

N3 - C'4-O'5 123.7 123.6 (-0.1) 124.2 (0.5)

N3 - C'4-H7 113.3 116.2 (2.9) 112.9 (-0.4)

O'5 - C'4-H7 122.9 120.2 (-2.7) 122.9 (0.0)

Torsions (degrees)

O'1 - C'2-N3 - C'4 180.0 180.0 (0.0) 180.0 (0.0)

O'1 - C'2-N3 - H*8 0.0 0.0 (0.0) 0.0 (0.0)

H6 - C'2-N3 - C'4 0.0 0.0 (0.0) 0.0 (0.0)

H6 - C'2-N3 - H*8 180.0 180.0 (0.0) 180.0 (0.0)

C'2 - N3 - C'4 - O'5 180.0 180.0 (0.0) 180.0 (0.0)

C'2 - N3 - C'4 - H7 0.0 0.0 (0.0) 0.0 (0.0)

H*8 - N3 - C'4 - O'5 0.0 0.0 (0.0) 0.0 (0.0)

H*8 - N3 - C'4 - H7 180.0 180.0 (0.0) 180.0 (0.0)

O'1 - C'2-N3 - H6 0.0 0.0 (0.0) 0.0 (0.0)

C'2 - N3 - H*8 - C'4 0.0 0.0 (0.0) 0.0 (0.0)

(22)

Table II.I. Comparison of Butyrolactam Structures Optimized by Ab Initio Calculation (HF/6-31G*) and by the HDFF and QMFF Force Fields.

Structures

Bonds (Å)

C'1 - C2 1.533 1.527 (-0.006) 1.527

C'1 - N4 1.358 1.384 (0.027) 1.354

C'1 - O'5 1.186 1.189 (0.002) 1.186

C2 - C3 1.549 1.533 (-0.016) 1.542

C2 - H6 1.082 1.085 (0.003) 1.080

C2 - H7 1.082 1.085 (0.003) 1.080

C3 - N4 1.455 1.429 (-0.026) 1.450

C3 - H8 1.083 1.086 (0.003) 1.082

C3 - H9 1.083 1.086 (0.003) 1.082

N4- H*10 0.996 0.999 (0.003) 0.994

Angles (degrees)

C2 - C'1 - N4 91.2 93.9 (2.8) 91.2 (0.0)

C2 - C'1 - O'5 135.9 134.3 (-1.6) 136.2 (0.3)

N4 - C'1 - O'5 133.0 131.8 (-1.2) 132.7 (-0.3)

C'1 - C2 - C3 85.7 82.5 (-3.1) 85.7 (0.0)

C'1 - C2 - H6 114.1 116.0 (1.9) 113.5 (-0.6)

C'1 - C2 - H7 114.1 116.0 (1.9) 113.5 (-0.6)

C3 - C2 - H6 115.7 115.0 (-0.7) 116.2 (0.4)

C3 - C2 - H7 115.7 115.0 (-0.7) 116.2 (0.4)

H6 - C2 - H7 109.9 110.1 (0.2) 110.1 (0.2)

C2 - C3 - N4 86.9 91.9 (4.9) 87.1 (0.1)

C2 - C3 - H8 115.3 115.2 (-0.1) 115.5 (0.2)

C2 - C3 - H9 115.3 115.2 (-0.1) 115.5 (0.2)

N4 - C3 - H8 114.1 109.3 (-4.8) 113.1 (-1.0)

N4 - C3 - H9 114.1 109.3 (-4.8) 113.1 (-1.0)

H8 - C3 - H9 109.7 113.6 (3.9) 110.8 (1.1)

C'1 - N4 - C3 96.2 91.7 (-4.6) 96.1 (-0.1)

C'1 - N4 - H*10 131.0 137.5 (6.5) 130.5 (-0.4)

C3 - N4 - H*10 132.8 130.8 (-2.0) 133.4 (0.6)

Torsions (degrees)

N4 - C'1 - C2 - C3 0.0 0.0 (0.0) 0.0 (0.0)

N4 - C'1 - C2 - H6 116.3 114.3 (-2.1) 116.7 (0.4)

N4 - C'1 - C2 - H7 243.7 245.7 (2.1) 243.3 (-0.4)

O'5 - C'1 - C2 - C3 180.0 180.0 (0.0) 180.0 (0.0)

O'5 - C'1 - C2 - H6 296.3 294.3 (-2.1) 296.7 (0.4)

O'5 - C'1 - C2 - H7 63.7 65.7 (2.1) 63.3 (-0.4)

(23)

C2 - C'1 - N4 - H*10 180.0 180.0 (0.0) 180.0 (0.0)

O'5 - C'1 - N4 - C3 180.0 180.0 (0.0) 180.0 (0.0)

O'5 - C'1 - N4 - H*10 0.0 0.0 (0.0) 0.0 (0.0)

C'1 - C2 - C3 - N4 0.0 0.0 (0.0) 0.0 (0.0)

C'1 - C2 - C3 - H8 244.7 247.6 (2.9) 245.8 (1.1)

C'1 - C2 - C3 - H9 115.3 112.4 (-2.9) 114.2 (-1.1)

H6 - C2 - C3 - N4 245.3 244.7 (-0.6) 245.9 (0.6)

H6 - C2 - C3 - H8 130.0 132.3 (2.3) 131.7 (1.7)

H6 - C2 - C3 - H9 0.6 357.1 (-3.5) 0.2 (-0.4)

H7 - C2 - C3 - N4 114.7 115.3 (0.6) 114.1 (-0.6)

H7 - C2 - C3 - H8 359.4 2.9 (3.5) 359.8 (0.4)

H7 - C2 - C3 - H9 230.0 227.7 (-2.3) 228.3 (-1.7)

C2 - C3 - N4 - C'1 0.0 0.0 (0.0) 0.0 (0.0)

C2 - C3 - N4 - H*10 180.0 180.0 (0.0) 180.0 (0.0)

H8 - C3 - N4 - C'1 116.4 117.6 (1.1) 116.5 (0.1)

H8 - C3 - N4 - H*10 296.4 297.6 (1.1) 296.5 (0.1)

H9 - C3 - N4 - C'1 243.6 242.4 (-1.1) 243.5 (-0.1)

H9 - C3 - N4 - H*10 63.6 62.4 (-1.1) 63.5 (-0.1)

C2 - C'1 - N4 - O'5 0.0 0.0 (0.0) 0.0 (0.0)

C'1 - N4 - C3 - H*10 0.0 0.0 (0.0) 0.0 (0.0)

Table III.A. Comparison of Formamide Frequencies Obtained by Ab Initio Calculation (HF/6-31G*) and the HDFF and QMFF Force Fields.

Frequencies

HF/6-31G* HDFF QMFF Mode

3971.7 3997.6 (25.9) 3958.4 (-13.4) NH asym stretch

3837.1 3875.0 (37.9) 3825.4 (-11.7) NH sym stretch

3213.3 3150.0 (-63.3) 3229.0 (15.7) C'H stretch

1998.4 1988.2 (-10.2) 1991.0 (-7.4) C'O' stretch

1788.7 2055.6 (266.9) 1806.0 (17.2) NH2 bend

1563.0 1498.2 (-64.8) 1529.0 (-34.0) C'H rock

1378.6 1168.6 (-210.0) 1333.7 (-44.8) C'N stretch

1182.5 1276.8 (94.3) 1230.5 (48.0) C'O' oop deformation

1159.9 933.4 (-226.5) 1116.8 (-43.1) NH2 rock

673.4 679.5 (6.1) 697.2 (23.8) C'N torsion

617.6 578.3 (-39.3) 627.3 (9.7) C'O' rock

(24)

Table III.B. Comparison of Planar Acetamide Frequencies Obtained by Ab Initio Calculation (HF/6-31G*) and the HDFF and QMFF Force Fields.

Frequencies

3975.1 3997.6 (22.5) 3970.0 (-5.1) NH asym stretch

3843.4 3873.9 (30.6) 3829.1 (-14.3) NH sym stretch

3337.2 3268.7 (-68.5) 3308.6 (-28.7) CH3 asym stretch

3272.1 3259.2 (-12.9) 3265.5 (-6.5) CH3 asym stretch

3214.4 3140.7 (-73.7) 3226.7 (12.3) CH3 sym stretch

1985.2 1974.8 (-10.4) 2004.3 (19.0) C'O' stretch

1795.0 2049.8 (254.8) 1799.8 (4.9) NH2 bend

1627.2 1624.8 (-2.4) 1692.9 (65.7) CH3 asym deformation

1617.2 1623.3 (6.1) 1681.7 (64.5) CH3 asym deformation

1562.3 1543.3 (-19.0) 1619.7 (57.5) CH3 sym deformation

1463.6 1324.0 (-139.6) 1485.5 (21.9) C'N stretch

1234.2 1083.8 (-150.4) 1151.6 (-82.7) NH2 rock

1168.9 1042.5 (-126.4) 1143.8 (-25.1) CH3 rock

1076.6 1001.5 (-75.1) 1060.5 (-16.1) CH3 rock

913.0 733.5 (-179.5) 886.4 (-26.6) C'C stretch

598.1 558.2 (-39.9) 605.7 (7.6) C'O' rock

562.6 641.6 (79.0) 614.1 (51.5) C'N torsion

446.6 356.5 (-90.1) 403.7 (-42.9) C'C rock

11.7 -6.5a,b_(-18.2) _{118.0 (106.3)} _CH

3 torsion

-144.5a _{175.9 (320.4)} _{380.8 (525.3)} _{amino inversion}

a_{The minus sign indicates that the frequency was calculated from the absolute value of a negative} eigenvalue. b_{This imaginary frequency arises from selecting the force field stationary state with} the geometry closest to the corresponding ab initio structure for comparison. In this case the configuration computed with the force field corresponds to a transition state.

Table III.C. Comparison of Planar Trans N-Methylformamide Frequencies Obtained by Ab Initio

Calculation (HF/6-31G*) and the HDFF and QMFF Force Fields.

Frequencies

3900.8 3934.0 (33.2) 3867.0 (-38.3) NH stretch

(25)

3296.9 3262.8 (-34.1) 3255.2 (-41.7) CH3 asym stretch

3230.5 3142.0 (-88.6) 3207.0 (-23.5) CH3 sym stretch

3206.7 3149.2 (-57.5) 3235.7 (28.9) C'H stretch

1977.2 1994.6 (17.4) 1978.5 (1.3) C'O' Stretch

1694.9 1792.2 (97.3) 1699.2 (4.2) NH rock

1655.1 1617.8 (-37.3) 1653.2 (-1.9) CH3 asym deformation

1609.3 1586.9 (-22.4) 1601.2 (-8.2) CH3 sym deformation

1559.9 1487.6 (-72.3) 1529.4 (-30.5) C'H rock

1348.6 1113.1 (-235.4) 1304.3 (-44.2) C'N stretch

1283.7 1039.3 (-244.4) 1239.1 (-44.6) CH3 rock

1266.0 1034.3 (-231.7) 1269.5 (3.5) CH3 rock

1035.4 823.9 (-211.5) 1000.1 (-35.3) NC stretch

837.8 692.0 (-145.9) 812.8 (-25.0) C'O' rock

486.9 560.8 (73.9) 574.4 (87.5) C'N torsion

291.8 301.2 (9.4) 317.4 (25.6) NC rock

228.5 323.4 (94.9) 328.1 (99.6) amino inversion

-60.6a _-62.5a_{(-1.9) -136.5}a_(-75.9) _CH

3 torsion

a_{The minus sign indicates that the frequency was calculated from the absolute value of a negative} eigenvalue.

Table III.D. Comparison of Cis N-Methylformamide Frequencies Obtained by Ab Initio

Frequencies

3855.6 3941.0 (85.4) 3810.5 (-45.1) NH stretch

3299.0 3259.9 (-39.0) 3278.2 (-20.8) CH3 asym stretch

3268.8 3261.4 (-7.4) 3252.0 (-16.8) CH3 asym stretch

3215.4 3141.7 (-73.6) 3206.4 (-8.9) CH3 sym stretch

3201.4 3149.8 (-51.6) 3205.7 (4.3) C'H stretch

1988.8 2012.1 (23.3) 1988.0 (-0.8) C'O' stretch

1643.2 1748.2 (105.0) 1626.3 (-16.9) NH rock

1623.1 1595.2 (-27.9) 1638.1 (15.0) CH3 sym deformation

1542.4 1515.9 (-26.5) 1562.4 (20.1) C'H rock

1412.8 1049.9 (-362.9) 1386.1 (-26.7) C'N stretch

1270.2 1105.5 (-164.7) 1241.8 (-28.3) CH3 rock

1258.9 1024.2 (-234.7) 1241.0 (-18.0) CH3 rock

1096.1 953.9 (-142.1) 1068.9 (-27.1) NC stretch

(26)

648.6 631.0 (-17.6) 698.3 (49.7) C'N torsion

374.6 343.6 (-31.0) 345.5 (-29.1) NC rock

193.0 179.5 (-13.5) 215.3 (22.3) CH3 torsion

66.3 -50.8a_{(-117.1) -74.9}a_(-141.2) _{amino inversion}

Table III.E. Comparison of Trans N-Methylacetamide Frequencies Obtained by Ab Initio

Frequencies

3914.8 3934.0 (19.2) 3886.2 (-28.6) NH stretch

3307.6 3259.5 (-48.1) 3269.1 (-38.4) N-CH3 asym stretch

3301.9 3261.6 (-40.3) 3267.1 (-34.9) C'-CH3 asym stretch

3296.4 3265.0 (-31.4) 3280.5 (-15.9) C'-CH3 asym stretch

3295.9 3262.9 (-33.0) 3256.2 (-39.7) N-CH3 asym stretch

3229.0 3142.0 (-87.0) 3207.7 (-21.3) N-CH3 sym stretch

3223.7 3140.9 (-82.8) 3222.0 (-1.6) C'-CH3 sym stretch

1956.5 1974.9 (18.4) 1973.3 (16.7) C'O' stretch

1711.0 1792.0 (81.0) 1707.0 (-4.0) NH rock

1658.9 1617.7 (-41.2) 1675.2 (16.2) N-CH3 asym deformation

1630.8 1627.0 (-3.8) 1650.4 (19.6) C'-CH3 asym deformation

1617.3 1626.3 (9.0) 1693.2 (75.9) C'-CH3 asym deformation

1609.1 1586.3 (-22.8) 1603.4 (-5.7) N-CH3 sym deformation

1555.2 1542.0 (-13.2) 1594.6 (39.4) C'-CH3 sym deformation

1408.2 1289.9 (-118.3) 1416.8 (8.6) C'-N stretch

1311.3 1044.3 (-267.0) 1249.8 (-61.4) N-CH3 rock

1265.7 1030.5 (-235.2) 1268.7 (3.0) N-CH3 rock

1191.5 1007.8 (-183.7) 1116.5 (-75.0) N-C stretch

1172.2 1058.3 (-113.9) 1151.6 (-20.6) C'-CH3 rock

1094.9 1034.8 (-60.1) 1033.7 (-61.2) C'-CH3 rock

950.6 731.2 (-219.4) 932.8 (-17.8) C'-C stretch

673.6 605.8 (-67.8) 653.6 (-20.0) C'O' rock

456.5 381.9 (-74.6) 426.7 (-29.9) C'C rock

365.9 373.4 (7.5) 506.5 (140.6) C'N torsion

284.0 266.6 (-17.4) 290.8 (6.8) NC rock

168.1 206.6 (38.5) 190.2 (22.1) amino inversion

19.8 -55.5a,b_(-75.3) _-110.4a,b_(-130.2) _C'-CH

3 torsion -41.4a _-78.5a_{(-37.1) -127.0}a_(-85.6) _N-CH

(27)

Table III.F. Comparison of Cis Planar N-Methylacetamide Frequencies Obtained byAb Initio

Frequencies

3872.7 3940.6 (67.9) 3831.3 (-41.4) NH stretch

3337.8 3268.6 (-69.2) 3305.8 (-32.0) C'-CH3 asym stretch

3306.7 3258.8 (-47.9) 3263.7 (-43.1) N-CH3 asym stretch

3276.5 3258.6 (-17.9) 3267.2 (-9.3) C'-CH3 asym stretch

3260.8 3262.6 (1.8) 3259.1 (-1.8) N-CH3 asym stretch

3218.9 3140.4 (-78.5) 3227.3 (8.4) C'-CH3 sym stretch

3208.6 3141.8 (-66.8) 3208.0 (-0.6) N-CH3 sym stretch

1969.9 1985.1 (15.2) 1999.5 (29.6) C'O' stretch

1644.2 1608.4 (-35.8) 1643.0 (-1.2) N-CH3 asym deformation

1633.9 1583.5 (-50.4) 1634.7 (0.8) N-CH3 sym deformation

1626.7 1742.4 (115.7) 1589.0 (-37.7) NH rock

1562.4 1543.6 (-18.8) 1617.5 (55.1) C'-CH3 deformation

1469.5 1314.4 (-155.1) 1492.6 (23.1) C'-N stretch

1318.6 1056.7 (-261.9) 1242.7 (-75.9) N-CH3 rock

1260.9 1031.9 (-229.0) 1264.9 (4.0) N-CH3 rock

1193.1 1029.5 (-163.6) 1131.4 (-61.7) NC stretch

1166.8 1042.9 (-123.9) 1137.5 (-29.3) C'-CH3 rock

1093.9 1003.4 (-90.5) 1077.4 (-16.4) C'-CH3 rock

867.3 708.5 (-158.8) 838.7 (-28.6) C'C stretch

611.9 457.7 (-154.2) 598.0 (-14.0) C'O' rock

529.0 507.0 (-22.0) 495.1 (-33.9) C'C rock

508.3 594.3 (86.0) 477.9 (-30.4) C'N torsion

297.8 268.3 (-29.5) 295.0 (-2.7) NC rock

183.4 142.1 (-41.3) 195.1 (11.7) N-CH3 torsion

115.2 98.5 (-16.7) 166.1 (50.9) C'-CH3 torsion

(28)

Table III.G. Comparison of N,N-Dimethylformamide Frequencies Obtained by Ab Initio

Frequencies

3361.4 3261.1 (-100.3) 3293.8 (-67.7) CH3 asym stretch

3300.4 3264.4 (-36.0) 3290.6 (-9.8) CH3 asym stretch

3249.6 3259.4 (9.8) 3233.1 (-16.5) CH3 asym stretch

3248.6 3259.0 (10.4) 3234.2 (-14.4) CH3 asym stretch

3214.5 3148.5 (-66.0) 3208.6 (-5.8) C'H stretch

3201.1 3142.7 (-58.4) 3194.5 (-6.6) CH3 sym stretch

3196.2 3143.5 (-52.7) 3193.1 (-3.1) CH3 sym stretch

1961.1 2001.1 (40.0) 1974.2 (13.1) C'O' stretch

1626.7 1641.3 (14.6) 1666.4 (39.7) CH3 sym deformation

1592.2 1654.0 (61.8) 1670.9 (78.7) CH3 sym deformation

1586.8 1284.7 (-302.1) 1601.8 (14.9) C'N stretch

1557.1 1525.0 (-32.1) 1553.1 (-4.0) C'H rock

1404.6 1231.3 (-173.3) 1406.0 (1.4) NC asym stretch

1287.8 1042.6 (-245.2) 1273.9 (-13.9) CH3 rock

1239.0 1001.6 (-237.4) 1225.2 (-13.8) CH3 rock

1199.3 988.7 (-210.6) 1160.2 (-39.2) CH3 rock

1185.5 1028.8 (-156.7) 1180.7 (-4.8) CH3 rock

941.5 821.0 (-120.5) 909.7 (-31.8) NC sym stretch

711.9 586.9 (-125.0) 695.7 (- 16.2) C'O' rock

426.3 419.6 (-6.7) 402.1 (-24.2) CNC bend

351.2 307.3 (-43.9) 356.3 (5.1) CNC rock

346.1 394.9 (48.8) 352.0 (6.0) C'N torsion

242.7 258.8 (16.1) 243.1 (0.4) amino inversion

161.7 143.3 (-18.4) 83.4 (-78.2) CH3 sym torsion

83.9 87.8 (3.9) -127.2a,b_(-211.1) _CH

3 asym torsion

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the geometry closest to the corresponding ab initio structure for comparison. In this case the configuration computed with the force field corresponds to a transition state.

Table III.H. Comparison of Planar N,N-Dimethylacetamide Frequencies Obtained by Ab Initio

Frequencies

3379.0 3261.1 (-118.0) 3300.1 (-79.0) N-CH3 asym stretch

3357.1 3265.0 (-92.1) 3321.4 (-35.7) N-CH3 asym stretch

3338.9 3267.8 (-71.1) 3299.4 (-39.4) C'-CH3 asym stretch

3281.7 3258.1 (-23.6) 3267.4 (-14.3) C'-CH3 asym stretch

3241.3 3259.1 (17.8) 3228.7 (-12.6) N-CH3 asym stretch

3240.3 3258.2 (17.9) 3233.0 (-7.3) N-CH3 asym stretch

3221.5 3140.1 (-81.4) 3226.5 (5.0) C'-CH3 sym stretch

3203.2 3143.8 (-59.4) 3194.4 (-8.8) C'-CH3 sym stretch

3193.5 3145.3 (-48.2) 3191.9 (-1.6) N-CH3 sym stretch

1935.2 1968.4 (33.3) 1974.6 (39.4) C'O' stretch

1637.8 1669.2 (31.4) 1710.1 (72.3) N-CH3 sym deformation

1627.7 1610.9 (-16.8) 1703.5 (75.9) C'-CH3 asym deformation

1593.0 1371.7 (-221.3) 1621.9 (28.9) N-CH3 sym deformation

1581.6 1675.5 (93.9) 1690.5 (108.9) C'-N stretch

1538.5 1549.1 (10.6) 1569.1 (30.6) C'-CH3 sym deformation

1408.1 1242.1 (-166.0) 1423.2 (15.1) NC asym stretch

1313.6 1156.7 (-156.9) 1302.0 (-11.6) N-CH3 rock

1286.7 1034.1 (-252.6) 1269.5 (-17.1) N-CH3 rock

1237.5 997.6 (-239.8) 1219.5 (-18.0) N-CH3 rock

1182.2 1040.0 (-142.2) 1184.7 (2.5) N-CH3 rock

1164.0 1053.9 (-110.1) 1129.3 (-34.7) C'-CH3 rock

1126.8 1028.2 (-98.6) 1109.2 (-17.7) C'-CH3 rock

1053.6 966.5 (-87.1) 1021.5 (-32.2) NC sym stretch

789.1 678.5 (-110.7) 767.4 (-21.7) C'C stretch

639.1 564.8 (-74.2) 635.7 (-3.4) C'O' rock

500.7 390.0 (-110.8) 470.9 (-29.8) C'C rock

435.6 439.9 (4.3) 435.7 (0.2) CNC bend

348.3 321.6 (-26.7) 361.0 (12.8) CNC rock

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212.5 208.1 (-4.4) 230.0 (17.5) C'-CH3 torsion

143.1 145.8 (2.7) 128.7 (-14.5) C'N torsion

78.3 85.0 (6.7) -84.1a,b_(-162.5) _N-CH

3 torsion -62.8a _{10.9 (73.7) -171.2}a_(-108.4) _N-CH

3 torsion

Table III.I. Comparison of Urea Frequencies Obtained by Ab Initio Calculation (HF/6-31G*) and the HDFF and QMFF Force Fields.

Frequencies

3926.2 3989.0 (62.8) 3927.2 (1.0) NH asym stretch

3925.9 3996.5 (70.6) 3932.8 (6.9) NH asym stretch

3814.9 3884.8 (69.9) 3813.5 (-1.4) NH sym stretch

3810.8 3870.7 (59.9) 3801.9 (-8.9) NH sym stretch

2000.3 2037.0 (36.7) 1996.5 (-3.7) C'O' stretch

1811.9 1929.0 (117.1) 1726.5 (-85.4) NH2 asym bend

1805.5 1953.0 (147.5) 1755.0 (-50.5) NH2 sym bend

1550.2 1404.7 (-145.5) 1552.1 (1.8) C'N asym stretch

1303.6 1118.7 (-184.9) 1168.4 (-135.2) NH2 sym rock

1166.1 990.0 (-176.1) 1064.0 (-102.1) NH2 asym rock

1034.8 640.8 (-394.0) 947.2 (-87.6) C'N sym stretch

648.8 770.6 (121.8) 720.7 (71.9) asym amino inversion

629.9 541.3 (-88.6) 666.3 (36.4) C'O' rock

598.8 675.5 (76.7) 607.6 (8.8) sym amino inversion

514.2 498.3 (-15.9) 567.5 (53.3) NC'N bend

483.2 415.1 (-68.1) 435.5 (-47.6) asym C'N torsion

417.2 416.5 (-0.7) 452.3 (35.1) sym C'N torsion

Table III.J. Comparison of N-Formylformamide Frequencies Obtained by Ab Initio Calculation (HF/6-31G*) and the HDFF and QMFF Force Fields.

Frequencies

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3256.1 3152.0 (-104.1) 3228.4 (-27.7) C'H sym stretch

3232.7 3148.7 (-84.0) 3224.4 (-8.2) C'H asym stretch

2046.2 1993.8 (-52.4) 2010.4 (-35.8) C'O' sym stretch

2007.6 2017.5 (9.9) 1996.8 (-10.8) C'O asym stretch

1627.9 1534.7 (-93.2) 1570.2 (-57.7) NH rock

1584.9 1518.6 (-66.3) 1575.8 (-9.1) C'H sym rock

1488.2 1493.6 (5.4) 1483.4 (-4.9) C'H asym rock

1370.2 1133.2 (-237.0) 1311.5 (-58.7) C'N sym stretch

1294.4 992.4 (-302.0) 1305.6 (11.2) C'N asym stretch

1176.5 1240.9 (64.4) 1197.2 (20.7) C'O' asym oop deformation

1161.9 1220.6 (58.7) 1163.6 (1.7) C'O' sym oop deformation

777.1 856.5 (79.4) 803.6 (26.5) C'N asym torsion

687.2 680.5 (-6.7) 721.7 (34.5) C'O' asym rock

580.1 430.3 (-149.8) 570.7 (-9.4) C'O' sym rock

303.1 306.7 (3.6) 299.2 (-3.9) C'N sym torsion

275.7 301.4 (25.7) 325.9 (50.2) C'NC' bend

137.3 145.6 (8.3) 142.7 (5.4) amino inversion

Table III.K. Comparison of Butyrolactam Frequencies Obtained by Ab Initio Calculation (HF/6-31G*) and the HDFF and QMFF Force Fields.

Frequencies

3878.3 3937.5 (59.2) 3893.3 (15.0) NH stretch

3324.1 3267.3 (-56.8) 3318.1 (-5.9) CH asym stretch

3282.5 3276.7 (-5.8) 3295.6 (13.1) CH asym stretch

3268.7 3187.2 (-81.5) 3278.1 (9.4) CH sym stretch

3238.4 3175.4 (-62.9) 3247.6 (9.3) CH sym stretch

2057.2 2013.5 (-43.7) 2072.5 (15.3) C'O' stretch

1684.3 1705.0 (20.7) 1709.9 (25.6) CH2 scissor

1609.6 1647.6 (37.9) 1685.9 (76.2) CH2 scissor

1548.7 1203.2 (-345.5) 1449.2 (-99.5) NH rock

1457.9 1345.6 (-112.2) 1431.7 (-26.2) CH2 wag

1353.7 1136.7 (-217.0) 1186.9 (-166.8) CH2 wag

1310.9 1027.4 (-283.5) 1357.4 (46.5) CH2 twist

1304.7 955.5 (-349.1) 1291.6 (-13.0) C'N stretch

1264.2 1088.0 (-176.2) 1270.6 (6.4) CH2 twist

1170.5 1142.2 (-28.3) 1121.1 (-49.4) CH2 rock

1099.4 1783.6 (684.3) 1057.9 (-41.4) NC stretch

1056.5 862.4 (-194.1) 1095.9 (39.4) C'C stretch

965.5 774.6 (-190.9) 913.0 (-52.5) CC stretch

896.7 891.3 (-5.4) 906.5 (9.8) CH2 rock

817.1 519.6 (-297.4) 674.4 (-142.6) ring deformation

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518.5 554.4 (35.9) 530.4 (11.9) C'O' rock

407.6 -498.6a_(-906.2) _{556.5 (148.9)} _{ring puckering}

75.3 366.1 (290.7) 199.7 (124.4) amino inversion