supp_b_1.doc 708KB Jun 05 2011 09:30:50 PM

Dr. H. Baumann

Tel: (01) 632 2901

FAX: (01) 632 1280

e-mail: baumann@org.chem.ethz.ch

Supplementary Material

Semiempirical Computation of Large Organic Structures and their UV/vis Spectra:

Program Discription and Application to Poly(triacetylene) Hexamer and Taxotere



by Harold Baumann*, Rainer E. Martin and François Diederich

Laboratorium für Organische Chemie der Eidgenössischen Technischen Hochschule,

Universitätstr. 16, CH-8092 Zürich

Procedure sido.c

1

Interactions between the doubly and singly excited configurations and between the

doubly excited and the ground configuration.

1 

hhl ll 1

0

| H| = (hl | hl)

  

(1)

 1_hhlm| H| 1₀ = 2(hl | hm)

(2)

1hk 0  2

mm_{| H|} 1 _{(hm | km)}

(3)





1  

0

_hklm_{| H|} 1 _{(hm | kl) + (hl | km)}

(4)





1hk 0  3 

lm 1

| H| (hm | kl) (hl | km)

(5)

1_hhll | H| 1s_r 0

(6)

1hhll | H| 1rl  2(hl | hr)

(7)

1_{ }   ₂

hh ll 1

h s

| H| (hl | ls)

(8)









  





1 hh

1

hl

i n

| H| = 2 H + 2 2(ii | hl) (ih | il) +

2 (ll | hl) (hh | hl)

ll  _hl

(9)

 1_kklm| H| 1_rs 0

(10)

1kklm| H| 1rl (km | rk)

(11)

1_kklm| H| 1_rm (kl | rk)

(12)

1_kklm| H|1  (kl | ms) + (km | ls) k

s



(13)

1kklm| H| 1km F + (mk | lm ) (kl | kk) + (kl | mm) lk 

(14)

1lm_kk| H| 1_kl F_mk + (lk | lm ) (km | kk) + (km | ll) 

(15)

1_hkmm| H| 1s_r 0

(16)

1hkmm| H| 1rm (km | hr) + (mh | kr)

(17)

1_hkmm| H|_ 1s_k (mh | ms)

(18)

1_hkmm| H|1  (mk | ms) h

s



(19)

1_hkmm| H|1_km F + (mk | hk ) + (mh | kk) (mh | mm) 

mh



(20)

1_hkmm| H|1_hm F + (mh | hk) + (mk | hh) (mk | mm) 

mk



(21)

1_hklm| H|_ 1s_r 0

(22)





1hk   

lm 1 r

m ₁

2





1hk   

lm 1 r l ₁

2

| H| (kr | hm) + (hr | km)

(24)





1hk   

1 ₁

2

| H| (mk | ls ) + (lk | ms)

lm

h s



(25)





1_hklm 1   1

2

| H| h (mh | ls) + (lh | ms)

s

(26)





1hk      

lm 1 k

m ₁

2 lh

| H| F (mh | ml) + (lh | kk) (lh | mm) + (lk | hk)

(27)

1_hklm 1_kl  1   

2 mh

| H| [ F ( lh | ml) + (mh | kk)

(mh | ll) + ( mk | hk)]



(28)

1_hklm| H| _hm  [ F  ( mk | ml) + (lk | hh )

(lk | mm ) + (lh | hk)]

1 ₁

2 lk



(29)

1_hklm| H| _hl  [ F  ( lk | ml) + (mk | hh)

( mk | ll) + (mh | hk)]

1 ₁

2 mk



(30)

1lmhk| H| 1sr 0

(31)







1



_hklm

| H|

1



_rm

 

3

(lh | kr) (hr | lk)



2



(32)







1



_hklm

|H|

1



_rl

 

₃

(mh | kr) (hr | mk)



2



(33)







1



_hklm 1



_hs

 

3



2

| H|



(ms| kl) (sl | mk)

(34)







1



_hklm 1



s_k

 

3



2

|H|



(ms| hl) (sl |mh)

(35)

    



1_{ }

hk lm 1

k

m 3

2 lh

| H| [ F + (kk | lh) (mm | lh) + (ml | hm) (kl | hk)]



(36)

    



1_{ }

hk lm 1

k

l 3

2 mh

| H| [ F + (kk | mh) (ll | mh) + (ml | hl ) (km | hk)]



(37)

1_hklm| H| _hm  [ F + (hh | lk) (mm | lk) + (ml | mk)   

(hl | hk)]

1 3

2 lk



(38)

1_hklm| H| _hl  [ F + (hh | mk) (ll | mk) + (ml | lk) 

(hm | hk)]

1 3

2 mk



(39)

Procedure dodo.c

Interactions between the doubly excited configurations.

Type 1 - Type 1:

1_hhmm| H|_ 1ll_kk 0

(40)

1_hhmm| H| 1mm_kk  (hk | hk)

(41)

Type 1 - Type 2:

1_hhmm| H|_ 1ln_kk 0

(43)

1_{ }  

hh mm 1

hh ln

| H| 2 (lm | mn)

(44)

1_hhmm| H|_ 1_kkmn 0

(45)





1mmhh | H| 1hhmn  2 Fmn + (mm | mn) 2(hh | mn) + (hm | hn) 

(46)





1_{ }   

hh mm 1

hh lm

ml

| H| 2 F + (mm | ml ) 2(hh | ml) + (hm | hl)

(47)

Type 1 - Type 3:

1_{ }  ₀

hh mm

jk ll

| H|_ 1

(48)

1_hhmm| H|_ 1ll_jh 0

(49)

1_hhmm| H|_ 1_hkll  0

(50)

1_{ }  

hh

mm 1

jk mm

| H| 2 (jh | hk)

(51)





1hhmm| H| 1hkmm  2 Fhk  (hk | hh) + 2(hk | mm) (hm | km) 

(52)





1_hhmm| H|1_hjmm  2 F  (hj| hh ) + 2(hj| mm) (hm | jm)

hj



(53)

Type 1 - Type 4:

1_{ }  ₀

hh mm

jk

| H|_ 1 ln

(54)

1_hhmm| H|_ 1_jklm 0

(55)

1_hhmm| H|_ 1_hklm 2(hk | lm) (kl | mh) 

(56)

1_hhmm| H|_ 1_hkmn 2(hk | mn) (kn | mh) 

(57)

1_hhmm| H|_ 1_jnlm 2(jh | ml) (jl | mh)

(58)

1_hhmm| H|_ 1_jnmn 2(jh | mn) (jn | mh)

(59)

Type 1 - Type 5:

1_hhmm| H|_ 1ln_jk 0

(60)

1_{ }  ₀

hh mm

jk lm

| H|_ 1

(61)

1_hhmm| H|_ 1lm_hk  3 (kl | mh)

(62)

1_hhmm| H|_ 1_hkmn  3 (kn | mh)

(63)

1_{ }  

hh mm

jn lm

| H|_ 1 3 (jl | mh)

(64)

1_{ }  

hh mm

jn mn

Type 2 - Type 2:

1_hhlm| H|_ 1_kkno 0

(66)

1hhlm| H| 1hhno (ln | mo) + (lo | mn)

(67)

1_hhlm| H|_ 1lo_kk 0

(68)

1hh    

lm

hh lo

| H|1 F 2(hh | mo) + (hm | ho) + (ll | mo) + (lo | ml) mo



(69)

1_hhlm| H|1_hhnl  F  2(hh | mn) + (hm | hn) + (ll | mn) + (ln | ml) mn



(70)

1hh    

lm 1 hh mo

lo

| H| F 2(hh | lo) + (hl | ho) + (mm | lo) + (mo | ml)

(71)

1_hhlm| H|1_hhmn F  2(hh | ln) + (hl | hn) + (mm | ln) + (mn | ml) ln



(72)

1hhlm| H| 1lmkk (hk | hk)

(73)

Type 2 - Type 3:

1_{ }  ₀

hh lm

jk nn

| H|_ 1

(74)

1_hhlm| H|_ 1_hknn 0

(75)

1_hhlm| H|1  2(ml | hk) (mh | kl) 

hk ll



(76)

1_hhlm| H| 1_hkmm 2(ml | hk) (hl | km) 

(77)

1_{ }   

hh lm

jh ll

| H|_ 1 2(ml | hj) (jl | hm)

(78)

1lm_hh| H|_ 1_jhmm 2(ml | hj) (hl | jm)

(79)

Type 2 - Type 4:

1lm_hh| H|1  0

jk no



(80)

1_hhlm| H|_ 1mn_jk  0

(81)

1_hhlm| H|_ 1_hkno 0

(82)





1_{ }   

hh lm

hk mn

| H|_ 1 2 (ln | hk) 0.5(hl | kn)

(83)





1hh    

lm

hk mo

| H|_ 1 2 (lo | hk) 0.5(hl | ko)

(84)





1hh    

lm

hk nl

| H|_ 1 2 (mn | hk) 0.5(hm | kn)

(85)





1_{ }   

hh lm

hk lo

| H|_ 1 2 (mo | hk) 0.5(hm | ko)

(86)





1_hhlm| H|_ 1mn_jh   2 (ln | jh) 0.5(hl | jn)

(87)





1_{ }   

hh lm

jh mo

1_hhlm| H|_ 1_jhnl  2 (mn | jh) 0.5(mh | jn)

(89)





1_hhlm| H|_ 1lo_jh  2 (mo | jh) 0.5(mh | jo)

(90)





1_{ }   

hh lm

jh lo

| H|_ 1 2 (mo | jh) 0.5(mh | jo)

(91)

1_{ }  

hh lm

jk lm

| H|_ 1 2 (hj| hk)

(92)

    



1_{ }

hh lm

hk lm

| H| 2[(F (hh | hk) + (ll | hk) 0.5(kl | hl) + (mm | hk) 0.5(hm | km)]

1

hk



(93)

    



1_{ }

hh lm

hj lm

| H| 2 [F (hh | hj) + (ll | hj) 0.5(jl | hl) + (mm | hj) 0.5(hm | jm)]

1

hj



(94)

Type 2 - Type 5:

1_hhlm| H|_ 1no_jk 0

(95)

1_{ }  ₀

hh lm

jk nm

| H|_ 1

(96)

1_hhlm| H|_ 1_hkno 0

(97)



1



lm_hh

| H|

1



_hknm

 

3

(lh | nk)

2



(98)



1



_hhlm

|H|

1



_hkmo

 

₃

(lh |ok)

2



(99)



1



lm_hh

|H|

1



_hknl

 

₃

(mh | nk)

2



(100)



1



_hhlm

| H|

1



_hklo

 

3

(mh |ok)

2



(101)

1hh   

lm

jh nm

| H|1 3 (hl | jn)

2



(102)

1hh   

lm

jh mo

| H|1 3 (hl | jo)

2



(103)

1_{ }  

hh lm

jh nl

|H|1 3 (hm | jn)

2



(104)

1hh   

lm

jh lo

| H|1 ₃ (hm | jo)

2



(105)

1_hhlm| H|_ 1_jklm 0

(106)







1



_hhlm

| H|

1



_hklm

 

3

(hl| kl) (hm | km)



2



(107)

1hh    

lm

hj lm

| H|1 3 (hl | jl) (hm | jm)

2



(108)

Type 3 - Type 3:

1_{ }  ₀

hk mm

gj nn

| H|_ 1

(109)

1_hkmm| H|_ 1_gjmm (gh | jk) + (gk | hj)

(110)

1_hkmm| H|1_hjmm F  2(mm | jk) + (km | jm) + (hj| hk) + (hh | jk)

jk



(112)

1_hkmm| H|1_ghmm F  2(mm | gk) + (km | gm) + (gh | hk) + (hh | gk)

gk



(113)

1_{ }   

hk mm

jk mm

| H|1 F 2(mm | hj) + (hm | jm) + (kj| hk) + (kk | hj)

hj



(114)

1_hkmm| H|1_gkmm F  2(mm | hg) + (hm | gm) + (gk | hk) + (kk | hg)

hg



(115)

1_hkmm| H|_ 1_hknn 0

(116)

Type 3 - Type 4:

1_hkmm| H|_ 1_gjln 0

(117)

1_{ }  ₀

hk mm

hj

| H|_ 1 ln

(118)

1_{ }  ₀

hk mm

gj mn

| H|_ 1

(119)





1_{ }   

hk mm

hj mn

| H|1 ₁ (km | jn) 2(mn | jk) 2



(120)





1_hkmm| H|1_kjmn ₁ (hm | jn) 2(mn | jh)

2



(121)





1_hkmm| H|1_kjmn ₁ (hm | jn) 2(mn | jh) 

2



(122)





1_hkmm| H|1_ghmn ₁ (km | gn) 2(mn | gk)

2



(123)





1_hkmm| H|1_gkmn ₁ (hm |gn) 2(mn |gh)

2



(124)





1_hkmm| H|1_hjlm ₁ (km | jl) 2(ml | jk)

2



(125)





1_{ }    ₂

hk mm

kj

lm _{hm jl ml jh}

| H|1 ₁

2

 _{( | ) ( | )}

(126)





1_hkmm| H|1_ghlm ₁ (km | gl) 2(ml |gk) 

2



(127)





1_{ }   

hk mm

gk lm

| H|_ 1 2 (hm | gl) 2(ml | gh)

(128)

1_{ }  

hk mm

hk

| H|_ 1 ln 2 (ml | mn)

(129)

1_hkmm| H| _hk  [2F  2(hh | mn) + (hm | hn) 2(mn | kk)

+ (km | kn) + 2(mn | mm)]

1 ₁

2 mn

 ln

(130)

1_hkmm| H| _hklm  [2F  2(hh | ml) + (hm | hl) 2(lm | kk)

+ (km | lk) + 2(lm | mm)]

1 ₁

2 ml



(131)

Type 3 - Type 5:

1_{ }  ₀

hk mm

gj

| H|_ 1 ln

(132)

1_hkmm| H|_ 1_hjln 0

(133)

1_hkmm| H|_ 1_gjmn 0

(134)

1hk   

mm

hj lm

| H|1 3 (mk | lj)

2

1hk   

mm

kj lm

|H|1 3 (mh|lj)

2



(136)

1_{ }  

hk mm

gh lm

| H|1 3 (mk | lg)

2



(137)

1hk   

mm

gk lm

| H|1 3 (mh | lg)

2



(138)

1hk   

mm

hj mn

| H|1 3 (mk | nj)

2



(139)

1_hkmm| H|1_kjmn  ₃ (mh | nj)

2



(140)

1hk   

mm

gh mn

| H|1 3 (mk | ng)

2



(141)

1hk   

mm

gk mn

| H|1 3 (mh | ng)

2



(142)

1_hkmm| H|_ 1_hkln  0

(143)







1



_hkmm

|H|

1



_hkmn

 

₃

(km | kn) (hm | hn)



2



(144)







1



_hkmm

| H|

1



_hklm

 

3

(hm | hl) (km | kl)



2



(145)

Type 4 - Type 4

1_hklm| H|_ 1_gjno 0

(146)

1_hklm| H|_ 1_gjno 0

(147)

1_hklm| H|_ 1_hkno (ln | mo) + (lo | mn)

(148)

1_hklm| H|_ 1_hjlo (kj| mo) + 0.5(jo | mk)

(149)

1_hklm| H|_ 1_hjmo (kj| lo) + 0.5( jo | lk)

(150)

1_{ }  

hk lm

hj nl

| H|_ 1 (kj| mn) + 0.5(jn | mk)

(151)

1_hklm| H|_ 1_hjnm (kj| ln) + 0.5(jn | lk)

(152)

1_hklm| H|_ 1_ghlo (kg | mo) + 0.5(go | mk)

(153)

1_{ }  

hk lm

gh mo

| H|_ 1 (kg | lo) + 0.5(go | lk)

(154)

1_hklm| H|_ 1_ghnl (kg | mn) + 0.5(gn | mk)

(155)

1_hklm| H|_ 1_ghnm (kg | ln) + 0.5( gn | lk)

(156)

1_{ }  

hk lm

gk lo

| H|_ 1 (hg | mo) + 0.5( go | mh)

(157)

1_hklm| H|_ 1_gkmo (hg | lo) + 0.5(go | lh)

(158)

1_hklm| H|_ 1_gknl (hg | mn) + 0.5(gn | mh)

(159)

1_{ }  

hk

lm 1

gk nm

| H| (hg | ln) + 0.5(gn | lh)

(160)

1_{ }  

hk lm

kj lo

1_hklm| H|_ 1_kjmo (hj| lo) + 0.5(jo | hl)

(162)

1_hklm| H|_ 1_kjnl (hj| mn) + 0.5(jn | hm)

(163)

1_{ }  

hk lm

kj nm

| H|_ 1 (hj| ln) + 0.5 (jn | hl)

(164)

1_hklm| H|_ 1_gjlm (kj| lj) + 0.5(hj| gk)

(165)

1lm_hk| H| _hklo F  (hh | mo) (kk | mo) + 0.5(hm | ho) + 0.5(km | ko) + (ll | mo) + (ml | ol)

1

mo



(166)

1_hklm| H| _hkmo F  (hh | lo) (kk | lo) + 0.5(hl | ho) + 0.5 (kl | ko) + (mm | lo) + (ml | om)

1

lo



(167)

1_hklm| H| _hk F  (hh | mn) (kk | mn) + 0.5(hm | hn) + 0.5(km | kn) + (ll | mn) + (ml | nl)

1

mn

 ln

(168)

1_{ }    

hk lm

hk mn

| H| F (hh | ln) (kk | ln) + 0.5(hl | hn) + 0.5(kl | kn) + (mm | ln) + (ml | mn)

1

ln



(169)

1_{ }    

hk lm

hj lm

|H| F (hh|kj) (hk|hj) + 0.5 (kl| jl) + 0.5 (km| jm) +(ll|kj) +(mm|kj)

1

kj



(170)

1_hklm| H| _ghlm F  (hh | gk) (hk | gh) + 0.5 (kl | gl) + 0.5 (km | gm) + (ll | gk) + (mm | gk)

1

gk



(171)

1_hklm| H| lm_jk F  (kk | hj) (hk | jk) + 0.5(hl | jl) + 0.5(hm | jm) + (ll | hj) + (mm | hj)

1

hj



(172)

1_hklm| H| _gklm F  (kk | hg) (hk | gk) + 0.5(hl | gl) + 0.5(hm | gh) + (ll | gh) + (mm | gh)

1

hg



(173)

Type 4 - Type 5

1_hklm| H|_ 1_gjno 0

(174)

1_{ }  ₀

hk lm

hj no

| H|_ 1

(175)

1hklm| H| 1hkno 0

(176)

1_hklm 1_hjlo  3 2

| H| (km | oj)

(177)

1_hklm| H|1_hjmo  3 (kl | oj) 2



(178)

1_hklm| H|1_hj  3 (km | nj) 2

 ln

(179)

1_hklm| H|1_hjmn  ₃ (kl | nj) 2



(180)

1_hk 1   3 2

| H| (km |go)

lm

gh lo



(181)

1lm_hk 1_ghmo  3 2

| H| (kl |go)

(182)

1_hklm| H|1_gh  ₃ (km | gn) 2

 ln

(183)

1_hklm 1_ghmn  3 2

1_{ }  

hk lm

gk lo

|H|1 3 (hm |go)

2



(185)

1lm_hk 1_gkmo  3 2

| H| (hl |go)

(186)

1_hk 1   3 2

| H| (hm |gn)

lm

gk

 ln

(187)

1lmhk| H| 1gkmn  32(hl | gn)

(188)

1_hklm| H|1mo_jk   ₃ (hl |oj) 2



(189)

1_hklm| H|1_jk  3 (hm | nj) 2

 ln

(190)

1_hklm| H|_ 1_gjlm 0

(191)





1_hklm| H|1_gjno  3 (km | ko) (hm | ho) 

2



(192)





1hk    

lm 1 hk mo 3

2

|H| (kl | ko) (hl | ho)

(193)





1hk    

lm

hk

| H|1 3 (hm | hn) (km | kn)

2

 ln

(194)





1lm_hk| H|1_hkmn  ₃ (hl | hn) (kl | kn)

2



(195)





1lm_hk| H|1_hjlm  3 (jm | km) (kl | jl)

2



(196)





1_hklm| H|1_ghlm  ₃ (kl | gl) (gm | km)

2



(197)





1lm_hk| H|1lm_jk  3 (jm | hm) (hl | jl)

2



(198)





1lm_hk| H|1_gklm  3 (hl | gl) (gm | hm)

2



(199)





1hk     

lm

hk lm

| H|1 3 (mk| mk) + ( hl| hl) (kl| kl) (hm| hm)

2



(200)

Type 5 - Type 5:

1_hklm| H|_ 1_gjno 0

(201)

1_hklm| H|_ 1_hjno 0

(202)

1_hklm| H|_ 1_hkno (ln | mo) (lo | mn) 

(203)

1_{ }   

hk lm

hj lo

| H|1 ₃ (jo | mk) (jk | mo) 2



(204)

1_hklm| H|1_hjmo  ₃ (jo| kl) + (jk | lo) 2



(205)

1hk   

lm

hj

| H|1 ₃ (jn | km ) + (jk | mn) 2

 ln

(206)

1_hklm| H|1_hjmn ₃ (jn | kl) (jk | ln) 

2



(207)

1_hklm| H|1_ghlo  ₃ (go | km) + (gk | mo) 2



(208)

1_{ }   

hk lm

ghmo

| H|1 ₃ (go | kl) (gk | lo) 2



(209)

1lm| H|_ 1ln ₃ (gn | km) (gk | mn)

1_{ }   

hk lm

gh mn

| H|1 ₃ (gn | kl) (gk | ln) 2



(211)

1_hklm| H|1_gklo ₃ (go| hm ) (gh | mo)

2



(212)

1hk    

lm

gk mo

| H|1 ₃ (go| hl) (gh | lo) 2



(213)

1_hklm| H|1_gk  ₃ (gn | hm) (gh | mn) 

2

 ln

(214)

1_hklm| H|1_gkmn ₃ (gn | hl) (gh | ln) 

2



(215)

1_hklm| H|1_jklo  ₃ (jo | hm) (hj| mo) 

2



(216)

1_{ }   

hk lm

jk mo

| H|1 ₃ (jo | hl) (hj| lo) 2



(217)

1_hklm| H|1_jk ₃ (jn | hm) (hj| mn) 

2

 ln

(218)

1hk    

lm

jk mn

| H|1 ₃ (jn | hl) (hj| ln) 2



(219)

1_hklm| H|_ 1_gjlm (gh | jk) (hj| gk)

(220)

    



1

hk 

lm

hk lo

| H| F (hh | mo) + (hm | ho) (kk | mo) + (km | ko) + (ll | mo) (lo | lm)

1

mo 32 32



(221)

      



1

hk 

lm

hk mo

| H| F (hh| lo) (hl| ho) (kk| lo) (kl| ko)

(mm | lo) + (mo | lm) 1

lo 32 32



(222)

     



1

hk 

lm

hk

| H| F + (hh | mn) (hm | hn) (kk | mn) (km | kn) (ll | mn) + (ln | lm)

1

mn 32 32

 ln

(223)

    



1

_hklm| H| _hkmn F (hh| ln) + (hl| hn) (kk| ln) + (kl| kn) + (mm| ln) (mn| lm)

1

ml 32 32



(224)

    

 

1_{ }

hk lm

hj lm

| H| F (hh | jk) + (kl | jl) (mm | jk) + (jm | km) (ll | mn) (hk | hj)

1

jk 32 32



(225)

     



1_{ }

hk lm

gh lm

| H| F (hh | gk) (kl | gl) + (mm | gk) (gm | km) (ll | gk) + (hk | hg)

1

gk 32 32



(226)

1_{ }     

hk lm

jk lm

| H| F (kk | hj) (hl | jl) + (mm | hj) (jm | hm) + (ll | hj) + (hk | jk)

1

hj 32 32



(227)

   

 

1_{ }

hk lm

gk lm

| H| F + (kk | gh) + (hl | gl) (mm | gh) + (gm | hm) (ll | gh) (hk | gk)

1

gh 32 32



(228)

Procedure h.c

REFERENCE