Supplementary material for online version only for “The Effect of Diffuse Basis Functions on Valence
Bond Structural Weights” by John Morrison Galbraitha*, Andrew M. Jamesa, and Coleen T. Nemesb
Table 1b. BOVB Chirgwin-Coulson structural weights of H-F when the initial F atom
s-type basis function is included (not included) in the construction of VB orbitals. Bold indicates
counterintuitive weights.
HL
IF
IH
Dea
1. aug-cc-pVDZ
0.638 (0.625) 0.147 (0.233) 0.215 (0.141) 518.2 (513.6)
2. cc-pVDZ
0.640 (0.607) 0.218 (0.311) 0.142 (0.082) 480.7 (469.0)
3. 6-31++G(d,p)
0.558 (0.556) 0.365 (0.363) 0.078 (0.081) 500.9 (497.7)
4. aug-cc-pVDZb
0.620 (0.617) 0.281 (0.282) 0.099 (0.100) 489.1 (487.3)
a
Bond dissociation energies in kJ mol-1. Reference value 565±4 kJ mol-1 [42]
b
Single p-type and d-type polarization functions on H ( = 0.727) and F ( = 1.640) respectively.
Table 1c. BOVB Löwdin structural weights of H-F when the initial F atom
s-type basis function is included (not included) in the construction of VB orbitals. Bold indicates
counterintuitive weights.
HL
IF
IH
Dea
1. aug-cc-pVDZ
0.618 (0.571) 0.153 (0.253) 0.229 (0.175) 518.2 (513.6)
2. cc-pVDZ
0.618 (0.528) 0.223 (0.337) 0.158 (0.135) 480.7 (469.0)
3. 6-31++G(d,p)
0.511 (0.530) 0.427 (0.438) 0.040 (0.042) 500.9 (497.7)
4. aug-cc-pVDZb
0.555 (0.638) 0.300 (0.305) 0.057 (0.058) 489.1 (487.3)
a
Bond dissociation energies in kJ mol-1. Reference value 565±4 kJ mol-1 [42]
b
Single p-type and d-type polarization functions on H ( = 0.727) and F ( = 1.640) respectively.
Table 2b. VBSCF Chirgwin-Coulson structural weights of H-F when the initial F atom
s-type basis function is included (not included) in the construction of VB orbitals. Bold indicates
counterintuitive weights.
HL
IF
IH
Dea
1. aug-cc-pVDZ
0.645 (0.643) 0.289 (0.299) 0.066 (0.057) 518.2 (513.6)
2. cc-pVDZ
0.652 (0.643) 0.302 (0.314) 0.046 (0.043) 480.7 (469.0)
3. 6-31++G(d,p)
0.588 (0.586) 0.398 (0.402) 0.015 (0.012) 500.9 (497.7)
4. aug-cc-pVDZb
0.639 (0.639) 0.317 (0.320) 0.044 (0.040) 489.1 (487.3)
a
Bond dissociation energies in kJ mol-1. Reference value 565±4 kJ mol-1 [42]
b
Single p-type and d-type polarization functions on H ( = 0.727) and F ( = 1.640) respectively.
Table 2c. VBSCF Löwdin structural weights of H-F when the initial F atom
s-type basis function is included (not included) in the construction of VB orbitals. Bold indicates
counterintuitive weights.
HL
IF
IH
Dea
1. aug-cc-pVDZ
0.542 (0.538) 0.326 (0.337) 0.131 (0.125) 518.2 (513.6)
2. cc-pVDZ
0.536 (0.534) 0.324 (0.351) 0.013 (0.115) 480.7 (469.0)
3. 6-31++G(d,p)
0.529 (0.522) 0.470 (0.477) 0.001 (0.001) 500.9 (497.7)
4. aug-cc-pVDZb
0.531 (0.528) 0.353 (0.354) 0.116 (0.010) 489.1 (487.3)
a
Bond dissociation energies in kJ mol-1. Reference value 565±4 kJ mol-1 [42]
b
Single p-type and d-type polarization functions on H ( = 0.727) and F ( = 1.640) respectively.
Table 3b. BOVB//aug-cc-pVDZ and 6-31++G(d,p)a Chirgwin-Coulson structural weights of H-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IX
IH
1. H-OH
0.630 (0.650)
0.106 (0.147)
0.264 (0.232)
2. H-OHa
0.603 (0.608)
0.306 (0.295)
0.090 (0.097)
3. H-NH2
0.515 (0.617)
0.031 (0.071)
0.454 (0.312)
4. H-NH2a
0.646 (0.656)
0.233 (0.230)
0.120 (0.114)
5. H-CH3
-0.246 (0.343)
-0.002 (0.003) 1.248 (0.654)
6. H-CH3a
0.980 (0.694)
-0.092 (0.145) 0.112 (0.161)
b
Bond dissociation energies in kJ mol-1.
Reference
425.1 kJ mol-1 at 0K for H-OH, H-NH2 and H-CH3 respectively [42].
Deb
463.5 (458.3)
447.4 (443.6)
414.3 (407.6)
425.7 (419.0)
427.2 (420.5)
437.8 (419.1)
values 493.7±0.8,
431±8,
and
Table 3c. BOVB//aug-cc-pVDZ and 6-31++G(d,p)a Löwdin structural weights of H-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IX
IH
1. H-OH
0.615 (0.603)
0.110 (0.165) 0.275 (0.232)
2. H-OHa
0.534 (0.534)
0.344 (0.320) 0.048 (0.146)
3. H-NH2
0.515 (0.591)
0.044 (0.080) 0.441 (0.329)
4. H-NH2a
0.581 (0.547)
0.259 (0.272) 0.160 (0.180)
5. H-CH3
0.026 (0.342)
0.003 (0.004) 0.971 (0.653)
6. H-CH3a
0.756 (0.552)
0.039 (0.207) 0.021 (0.241)
b
Bond dissociation energies in kJ mol-1.
Reference
425.1 kJ mol-1 at 0K for H-OH, H-NH2 and H-CH3 respectively [42].
Deb
463.5 (458.3)
447.4 (443.6)
414.3 (407.6)
425.7 (419.0)
427.2 (420.5)
437.8 (419.1)
values 493.7±0.8,
431±8,
and
Table 4b. VBSCF//aug-cc-pVDZ and 6-31++G(d,p)a Chirgwin-Coulson structural weights of H-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IX
IH
1. H-OH
0.674 (0.676)
0.240 (0.244) 0.086 (0.080)
2. H-OHa
0.632 (0.637)
0.343 (0.339) 0.025 (0.024)
3. H-NH2
0.706 (0.707)
0.198 (0.200) 0.096 (0.092)
4. H-NH2a
0.677 (0.683)
0.276 (0.277) 0.046 (0.040)
5. H-CH3
0.749 (0.752)
0.146 (0.152) 0.105 (0.096)
6. H-CH3a
0.737 (0.738)
0.178 (0.183) 0.086 (0.079)
b
Bond dissociation energies in kJ mol-1.
Reference
425.1 kJ mol-1 at 0K for H-OH, H-NH2 and H-CH3 respectively [42].
Deb
463.5 (458.3)
447.4 (443.6)
414.3 (407.6)
425.7 (419.0)
427.2 (420.5)
437.8 (419.1)
values 493.7±0.8,
431±8,
and
Table 4c. VBSCF//aug-cc-pVDZ and 6-31++G(d,p)a Löwdin structural weights of H-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IX
IH
1. H-OH
0.549 (0.546)
0.292 (0.298) 0.041 (0.157)
2. H-OHa
0.514 (0.512)
0.379 (0.377) 0.108 (0.111)
3. H-NH2
0.542 (0.540)
0.271 (0.275) 0.187 (0.185)
a
4. H-NH2
0.524 (0.518)
0.333 (0.338) 0.142 (0.009)
5. H-CH3
0.529 (0.527)
0.252 (0.258) 0.219 (0.214)
6. H-CH3a
0.529 (0.526)
0.272 (0.278) 0.200 (0.196)
b
Bond dissociation energies in kJ mol-1.
Reference
425.1 kJ mol-1 at 0K for H-OH, H-NH2 and H-CH3 respectively [42].
Deb
463.5 (458.3)
447.4 (443.6)
414.3 (407.6)
425.7 (419.0)
427.2 (420.5)
437.8 (419.1)
values 493.7±0.8,
431±8,
and
Table 5b: BOVB//aug-cc-pVDZ and 6-31++G(d,p)a Chirgwin-Coulson structural weights of F-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IF
IX
Deb
1. F-OH
0.602 (0.613)
0.228 (0.277)
0.170 (0.110)
160.6 (153.9)
a
2. F-OH
0.602 (0.646)
0.254 (0.251)
0.144 (0.104)
158.9 (152.2)
3. F-NH2
0.609 (0.553)
0.178 (0.370)
0.213 (0.077)
255.8 (237.1)
4. F-NH2a
0.599 (0.577)
0.279 (0.350)
0.122 (0.073)
235.3 (224.1)
5. F-CH3
0.246 (0.505)
-0.032 (0.433) 0.786 (0.062)
428.5 (393.4)
6. F-CH3a
0.624 (0.505)
0.161 (0.442)
0.214 (0.053)
398.7 (379.7)
b
-1
Bond dissociation energies in kJ mol .
Reference values 268±13,
452 kJ mol-1 at 0K for F-OF, F-NF2 and F-CH3 respectively [42].
238±8,
and
Table 5c: BOVB//aug-cc-pVDZ and 6-31++G(d,p)a
Löwdin structural weights of F-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IF
IX
Deb
1. F-OH
0.586 (0.584)
0.234 (0.128) 0.180 (0.075)
160.6 (153.9)
2. F-OHa
0.579 (0.613)
0.261 (0.264) 0.160 (0.122)
158.9 (152.2)
3. F-NH2
0.608 (0.527)
0.178 (0.375) 0.214 (0.098)
255.8 (237.1)
a
4. F-NH2
0.577 (0.547)
0.286 (0.358) 0.089 (0.041)
235.3 (224.1)
5. F-CH3
0.342 (0.458)
0.087 (0.510) 0.539 (0.032)
428.5 (393.4)
6. F-CH3a
0.622 (0.480)
0.162 (0.441) 0.217 (0.078)
398.7 (379.7)
b
Bond dissociation energies in kJ mol-1.
Reference values 268±13,
452 kJ mol-1 at 0K for F-OF, F-NF2 and F-CH3 respectively [42].
238±8,
and
Table 6b: VBSCF//aug-cc-pVDZ and 6-31++G(d,p)a Chirgwin-Coulson structural weights of F-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IF
IX
Deb
1. F-OH
0.741 (0.737)
0.180 (0.198) 0.079 (0.065)
160.6 (153.9)
2. F-OHa
0.744 (0.742)
0.178 (0.192) 0.078 (0.066)
158.9 (152.2)
3. F-NH2
0.661 (0.654)
0.276 (0.311) 0.063 (0.036)
255.8 (237.1)
4. F-NH2a
0.661 (0.657)
0.288 (0.305) 0.051 (0.038)
235.3 (224.1)
5. F-CH3
0.601 (0.572)
0.341 (0.412) 0.058 (0.016)
428.5 (393.4)
6. F-CH3a
0.585 (0.561)
0.379 (0.424) 0.036 (0.015)
398.7 (379.7)
b
-1
Bond dissociation energies in kJ mol .
Reference values 268±13,
452 kJ mol-1 at 0K for F-OF, F-NF2 and F-CH3 respectively [42].
238±8,
and
Table 6c: VBSCF//aug-cc-pVDZ and 6-31++G(d,p)a
Löwdin structural weights of F-X
(X = -OH, -NH2, -CH3) when the initial heavy atom atom s-type basis function
is included (not included) in the construction of VB orbitals. Bold indicates counterintuitive weights.
HL
IF
IX:0
Deb
:q
1. F-OH
0.826 (0.682)
0.135 (0.222) 0.039 (0.096)
a
2. F-OH
0.689 (0.822)
0.108 (0.217) 0.039 (0.096)
3. F-NH2
0.619 (0.597)
0.292 (0.331) 0.089 (0.072)
4. F-NH2a
0.705 (0.601)
0.275 (0.325) 0.020 (0.073)
5. F-CH3
0.556 (0.511)
0.354 (0.424) 0.090 (0.065)
6. F-CH3a
0.532 (0.506)
0.392 (0.434) 0.075 (0.061)
b
Bond dissociation energies in kJ mol-1.
Reference
-1
452 kJ mol at 0K for F-OF, F-NF2 and F-CH3 respectively [42].
160.6 (153.9)
158.9 (152.2)
255.8 (237.1)
235.3 (224.1)
428.5 (393.4)
398.7 (379.7)
values 268±13,
238±8,
and