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Supplemental tables


Table 5.6: Ionization potentials of first row atoms; HF = Hartree-Fock/6-311g**
  new eFF energy (au)   ionization potentials (kcal/mol)
  E(Z) E(Z+1)   new eFF old eFF HF exact
H -0.424413 0   266.3 266.3 313.6 313.6
He -2.300987 -1.697653   378.6 378.6 540.8 567.0
Li -6.114980 -5.944908   106.7 105.6 123.1 124.3
Be -12.144527 -11.878010   167.2 165.8 185.6 215.0
B -20.634538 -20.359386   172.7 228.4 183.0 191.4
C -31.949192 -31.554495   247.7 155.3 249.1 259.7
N -46.398088 -45.919451   300.0 60.9 322.6 335.2
O -64.141692 -63.732720   257.1 421.1 276.3 314.0
F -85.639717 -85.082131   350.4 190.2 363.1 401.8
Ne -111.218594 -110.546393   421.9 -12.8 457.8 497.3



Table 5.7: Polarizabilities of first row atoms
  dipole (debye)   polarizability ( $ \mathrm{bohr^{3}}$)
  eFF   eFF $ \mathrm{\sigma_{1}}$ eFF $ \mathrm{\sigma_{2}}$ eFF $ \mathrm{\sigma_{3}}$ eFF avg $ \mathrm{\sigma}$ exact
H 0.000   3.1 3.1 3.1 3.1 4.5
He 0.000   0.7 0.7 0.7 0.7 1.4
Li 0.000   204.4 204.4 204.4 204.4 164.0
Be 0.000   51.5 51.4 51.4 51.5 37.8
B 0.001   42.7 42.5 23.9 36.4 20.4
C 0.001   39.2 8.7 8.2 18.7 11.9
N 0.000   4.5 4.5 4.4 4.5 7.4
O 0.071   37.4 5.9 2.9 15.4 5.4
F 0.338   79.7 24.6 5.0 36.4 3.8
Ne 0.000   1.1 1.1 1.1 1.1 2.7



Table 5.8: Atom hydride bond dissociation energies and geometries.
        BDE   bond length   bond angle
        (kcal/mol)   (angstroms)   (degrees)
  spin E (hartrees)   eFF exact   eFF exact   eFF exact
H d -0.424413                  
C t -31.94919                  
N q -46.39809                  
O t -64.14169                  
F d -85.63972                  
                     
CH d -32.5385   103.5 81.4   1.124 1.120      
NH t -46.97412   95.1 75.1   1.051 1.036      
OH d -64.74731   113.7 102.3   0.94 0.970      
FH s -86.24148   111.3 136.4   0.874 0.917      
                     
$ \mathrm{CH_{2}}$ t -33.11301   94.2 101.8   1.119 1.08   118.7 135.5
$ \mathrm{CH_{2}}$ s -33.130497   105.2 92.4   1.137 1.109   125.0 102.0
$ \mathrm{NH_{2}}$ d -47.55188   96.2 96.6   1.033 1.024   105.5 103.2
$ \mathrm{OH_{2}}$ s -65.3489   111.2 117.9   0.949 0.958   103.7 104.5
                     
$ \mathrm{CH_{3}}$ d -33.69142   96.6 109.6   1.133 1.079   112.5 120.0
$ \mathrm{NH_{3}}$ s -48.13353   98.7 101   1.044 1.017   104.5 107.8
                     
$ \mathrm{CH_{4}}$ s -34.23913   77.4 104.8   1.144 1.086   109.5 109.5



Table 5.9: Atom hydride dipole moments; MP2/cc-pvtz dipoles are from the NIST webbook.
    dipole (debye)
  spin eFF mp2 expt
H d 0.000    
C t 0.001    
N q 0.000    
O t 0.071    
F d 0.338    
       
CH d 1.258 1.539  
NH t 1.567 1.592  
OH d 2.559 1.702 1.660
FH s 2.769 1.824 1.820
       
$ \mathrm{CH_{2}}$ t 1.534 0.612  
$ \mathrm{CH_{2}}$ s 1.381 0.590  
$ \mathrm{NH_{2}}$ d 2.398 1.864  
$ \mathrm{OH_{2}}$ s 3.269 1.936 1.850
       
$ \mathrm{CH_{3}}$ d 1.256 0.000 0.000
$ \mathrm{NH_{3}}$ s 2.945 1.622 1.470
       
$ \mathrm{CH_{4}}$ s 0.000 0.000 0.000



Table 5.10: Atom hydride bond pair and lone pair geometry parameters; distances are in bohr and angles are in degrees.
  B3LYP/6-311g**   eFF
  $ \mathrm{d_{nuc \cdot bp}}$ $ \mathrm{d_{nuc \cdot lp}}$ $ \mathrm{\theta_{lp\cdot lp}}$   $ \mathrm{d_{nuc \cdot bp}}$ $ \mathrm{d_{nuc \cdot lp}}$ $ \mathrm{\theta_{lp\cdot lp}}$
$ \mathrm{CH_{4}}$ 1.375       1.452    
$ \mathrm{NH_{3}}$ 1.161 0.642     1.187 0.871
$ \mathrm{OH_{2}}$ 0.999 0.572 121.9   0.987 0.788 119.7
FH 0.861 0.508 114.5   0.830 0.696 113.4
Ne   0.456 109.5   0.613 109.5



Table 5.11: Bond dissociation and relative conformer energies of ethane, ethylene, and acetylene.
    $ \mathrm{\Delta E}$ (kcal/mol)
relative to energy of eFF exact
$ \mathrm{C_{2}H_{6}}$ 2 $ \mathrm{CH_{3}}$ (d) 140.4 89.7
$ \mathrm{C_{2}H_{4}}$ 2 $ \mathrm{CH_{2}}$ (t) 211.1 172.2
$ \mathrm{C_{2}H_{2}}$ 2 CH (d) 194.3 229.8
       
$ \mathrm{C_{2}H_{6}}$ $ \mathrm{C_{2}H_{5}}$ (d) + H (d) 75.9 100.1
$ \mathrm{C_{2}H_{4}}$ $ \mathrm{C_{2}H_{3}}$ (d) + H (d) 82.0 113.3
$ \mathrm{C_{2}H_{2}}$ $ \mathrm{C_{2}H}$ (d) + H (d) 105.2 131.8
       
$ \mathrm{C_{2}H_{6}}$ (staggered) $ \mathrm{C_{2}H_{6}}$ (eclipsed) 1.6 3.0
$ \mathrm{C_{2}H_{4}}$ (planar) $ \mathrm{C_{2}H_{4}}$ (twisted) 15.4 65.0



Table 5.12: Absolute energies of ethane, ethylene, acetylene, and related conformers and fragments.
  spin E (kcal/mol)
H d -0.424413
CH d -32.538497
$ \mathrm{CH_{2}}$ t -33.113010
$ \mathrm{CH_{3}}$ d -33.691424
$ \mathrm{C_{2}H_{5}}$ d -67.061321
$ \mathrm{C_{2}H_{3}}$ d -66.007466
$ \mathrm{C_{2}H}$ d -64.794602
   
$ \mathrm{C_{2}H_{6}}$ (staggered) s -67.606657
$ \mathrm{C_{2}H_{6}}$ (eclipsed) s -67.604039
$ \mathrm{C_{2}H_{4}}$ (planar) s -66.562498
$ \mathrm{C_{2}H_{4}}$ (twisted) s -66.538012
$ \mathrm{C_{2}H_{2}}$ s -65.386616



Table 5.13: Bond lengths of ethane, ethylene, acetylene, and related conformers and fragments.
      $ \mathrm{d_{CC}}$ ( $ \mathrm{\AA}$)   $ \mathrm{d_{CH}}$ ( $ \mathrm{\AA}$)
  spin   eFF B3LYP exact   eFF B3LYP exact
H d                
CH d           1.124 1.128 1.120
$ \mathrm{CH_{2}}$ t           1.119 1.080 1.085
$ \mathrm{CH_{3}}$ d           1.133 1.080 1.079
$ \mathrm{C_{2}H_{5}}$ d   1.512 1.487     1.129 1.083  
$ \mathrm{C_{2}H_{3}}$ d   1.319 1.305 1.316   1.141 1.088 1.085
$ \mathrm{C_{2}H}$ d   1.196 1.202 1.217   1.110 1.064 1.047
                 
$ \mathrm{C_{2}H_{6}}$ (staggered) s   1.530 1.531 1.536   1.141 1.093 1.091
$ \mathrm{C_{2}H_{6}}$ (eclipsed) s   1.533 1.544     1.140 1.092  
$ \mathrm{C_{2}H_{4}}$ (planar) s   1.335 1.327 1.339   1.138 1.085 1.086
$ \mathrm{C_{2}H_{4}}$ (twisted) s   1.345 1.327     1.137 1.085  
$ \mathrm{C_{2}H_{2}}$ s   1.209 1.198 1.203   1.120 1.063 1.063



Table 5.14: Bond angles of ethane, ethylene, acetylene, and related conformers and fragments.
      $ \mathrm{a_{HCH}}$ (degrees)   $ \mathrm{a_{HCH}}$ radical end (degrees)
  spin   eFF B3LYP exact   eFF B3LYP exact
H d                
CH d                
$ \mathrm{CH_{2}}$ t           118.7 134.7 135.5
$ \mathrm{CH_{3}}$ d           112.5 120.0 120.0
$ \mathrm{C_{2}H_{5}}$ d   108.1 108.2     110.2 117.5  
$ \mathrm{C_{2}H_{3}}$ d   124.6 115.9 121.5   127.5 138.5 137.3
$ \mathrm{C_{2}H}$ d                
                 
$ \mathrm{C_{2}H_{6}}$ (staggered) s   107.4 107.6 108.0        
$ \mathrm{C_{2}H_{6}}$ (eclipsed) s   107.0 107.1          
$ \mathrm{C_{2}H_{4}}$ (planar) s   119.5 116.4 117.6        
$ \mathrm{C_{2}H_{4}}$ (twisted) s   114.4 116.5          
$ \mathrm{C_{2}H_{2}}$ s                



Table 5.15: Heteroatom single, double, and triple bonded species bond dissociation energies and bond lengths.
        BDE (kcal/mol)   bond length ( $ \mathrm{\AA}$)
  spin E (hartrees)   eFF exact   eFF exact
O s -64.102759            
O t -64.141692            
N d -46.315322            
F d -85.620743            
                 
NH s -32.538497            
OH d -64.747313            
NH t -46.974123            
                 
$ \mathrm{CH_{2}}$ t -33.11301            
$ \mathrm{NH_{2}}$ d -47.551883            
                 
$ \mathrm{CH_{3}}$ d -33.691424            
                 
$ \mathrm{C_{2}H_{6}}$ s -67.606657   140.4 89.6   1.530 1.528
$ \mathrm{N_{2}H_{4}}$ s -95.41651   196.2 68.2   1.329 1.413
$ \mathrm{O_{2}H_{2}}$ s -129.873617   237.8 51.2   1.169 1.396
$ \mathrm{F_{2}}$ s -171.679689   275.0 37.9   1.045 1.345
$ \mathrm{O_{2}}$ t -128.650873   255.0 163.4   1.137 1.208
                 
$ \mathrm{C_{2}H_{4}}$ s -66.562498   211.1 172.2   1.335 1.317
$ \mathrm{N_{2}H_{2}}$ s -94.382841   272.7 144.0   1.146 1.216
$ \mathrm{O_{2}}$ s -128.85089   356.1 96.0   1.003 1.216
                 
$ \mathrm{C_{2}H_{2}}$ s -65.386616   194.3 229.7   1.209 1.186
$ \mathrm{N_{2}}$ s -93.007331   236.4 334.9   1.052 1.078


next up previous contents
Next: Bibliography Up: Development of an electron Previous: Conclusion   Contents
Julius 2008-04-29