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ZINDO Parameters eGVisualization of Chromophore  YCAbsorption Intensity ~ Overlap Vibrational Fine Structure aEGradient Affects Band Width Band Width Estimation gHFluorescence Spectra iIFluorescein (dibasic) Spectra  kJCalculating Spectra with CAChe Safe Laboratory ProcedurelIs the instrument working? Do I know how to use it? Is this instrument appropriate for the current research?mmExperimental vs Calculated   n -> p* Transition of C=O8 UV of Monosubstituted Benzenes  0Anthraquinones for Thermal Transfer Wax Printing11# !Calculated vs. Experimental "Anthraquinone Calibration   #What s Wrong? Is ZINDO right? What is ZINDO calculating? Are we comparing the right absorptions? Is solvation a factor? Is aggregation a problem? Are the structures right? Which is best geometry/conformation to use? Experimental data correct?$Is ZINDO right?Lliterature absolute accuracy relative accuracy zero-point energy correctionsMM%Literature Background The literature suggests that at visible wavelengths the standard deviation of the [INDO/S] calculation is between 15 and 35 nm.  l-maxima calculations using INDO seem useful when the geometries including dihedral angles are correct. 0xh& Dye Calibrations '!More Dye Calibrations ("Linear Fused Aromatic Rings )#Linear Fused Aromatic Rings +%What Geometry Did We Calculate?  ,&Does the Geometry Matter? -'Which structure is right? .(Sensitivity to Model /)Processing Times 0*Force a flat structure 1+Effect of Ring Geometry 2,Effect of Ring & Amine Geometry  *$Methanol Solvation?  3-Anthraquinone Calibration   4.Effect of Calibration 5/ Conclusions lINDO/S can be calibrated so that it is useful for predicting UV/visible spectra of dyes. (ZINDO predictions are systematically too short.) Calculated spectra are sensitive to molecular geometry. Best results are obtained with experimental geometries. Vibrational structure can confuse spectral assignments. Excited state gradients correlate with band widths. mm60Chemistry Today 71Chemistry by Simulation 82Chemistry by Design 93Summary Points=You learn something almost every time you view a molecule a new way Safe laboratory procedure: calibrate before use Bootstrap from small problems to large problems Stretch beyond simulation of experiment to interpretation. Valuable insight will come from understanding why experiments and calculations do not agree4>b ZINDO Capabilities  ZINDO Limitations Background References for ZINDO  BZINDO is a semi-empirical SCF/CI package including analytical gradient optimization developed by Prof. M. C. Zerner from the University of Florida. ZINDO is based upon the INDO approximations of Pople, Santry and Segal: Pople, Santry, Segal J. Chem. Phys. 43, S129 (1965) Pople, Segal J. Chem. Phys. 43, S136 (1965) Pople, Segal J. Chem. Phys. 44, 3289 (1966) Santry, Segal J. Chem. Phys. 47, 158 (1967) Santry J. Amer. Chem. Soc. 90, 13 (1968) The original INDO method has been enhanced by Prof. Zerner to include spectroscopic parameterization, configuration interaction, higher angular momentum orbitals (d-orbitals), and analytical gradients: Ridley, Zerner , Theoret. Chim. Acta. 32, 111 (1973) Ridley, Zerner, Theoret. Chim. Acta. 42, 223 (1976) Ridley, Zerner, Theoret. Chim. Acta. 53, 21 (1979) Zerner, Loew, Kirchner, Mueller-Westerhoff, J. Amer. Chem. Soc. 102, 589 (1980) Head, Zerner, Chem. Phys. Lett. 32, 246 (1985) Head, Zerner, Chem. Phys. Lett. 131, 359 (1986) Anderson, Edwards, Zerner, Inorg. Chem. 25, 2728 (1986) Edwards, Zerner, Theoret. Chim. Acta. 72, 347 (1987)dPPPP~mQ '('&V ,%!Applications of ZINDOh1. J. Ridley and M. C. Zerner, Theoret. Chim. Acta (Berl.) 72, 111-134 (1973)"An Intermediate Neglect of Differential Overlap Technique for Spectroscopy: Pyrrole and the Azines". 2. W. P. Anderson, W. Daniel Edwards, and Michael C. Zerner, Inorg. Chem. 1986, 25 2728-2732, "Calculated Spectra of Hydrated Ions of the First Transition-Metal Series." 3. W. Daniel Edwards, Brian Weiner and Michael C. Zerner, J. Am. Chem. Soc, 1986, 108, 2196-2204, "On the Low-Lying States and Electronic Spectroscopy of Iron(II) Porphine." 4. Ralph S. Becker, L. V. Natarajan, Christian Lenoble, and Ronald G. Harvey, J. Am. Chem. Soc. 1988, 110, 7163-7167, "Photophysics, Photochemistry and Theoretical Calculations of Some Benz[a]anthracene-3,4,-diones and Their Significance." 5. Jikang Feng, Jerzy Leszczynski, Brian Weiner, and Michael C. Zerner, J. Am. Chem. Soc, 1989, 111, 4648-4655, "The Reaction C3H3+ + C2H2 and the Structural Isomers of C5H5+." 6. Frank U. Axe, Charles Flowers, Gilda H. Loew, and Ahmad Walch, J. Am. Chem. Soc., 1989, 111, 7333-7339, "Theoretical Studies of High-, Intermediate-, and Low-Spin Model Heme Complexes."id jb 8k  A p  l  Applications of ZINDO (cont) 7. Manfred Kotzian, Notker Rosch, Hartmut Schroder, and Michael C. Zerner, J. Am. Chem. Soc., 1989, 111, 7687-7696, "Optical Spectra of Transition-Metal Carbonyls" Cr(CO)6, Fe(CO)5, and Ni(CO)4." 8. Wayne P. Anderson, Thomas R. Cundari, Russell S. Drago, Michael C. Zerner, Inorg. Chem. 29, 1, 1990, "Utility of the Semiempirical INDO/1 Method for the Calculation of the Geometries of Second-Row Transition Metal Species." 9. David R. Kanis, Mark A. Ratner, and Tobin J. Marks, J. Am. Chem. Soc., 1990, 112, 8203-8204, "Description of Quadratic Optical Nonlinearities for Transition-Metal Organometallic Chromophores Using an SCF-LCAO MECI Formalism." 10. Mati Karelson and M. C. Zerner, J. Am. Chem. Soc., 1990, 112, 9405-9408, "On the n-a* Blue Shift Accompanying Solvation." 11. Yuji Kubo, Katsuhira Yoshida, Masafumi Adachi, Shimichiro Nakamura, and Shuichi Maeda, J. Am. Chem. Soc. 1991, 113, 2868-2873, "Experimental and Theoretical Study of Near-Infrared Absorbing Naphthoquinone Methide Dyes with Nonplanar Geometry." 12. Masafumi Adachi and Shinichiro Nakamura, Dyes and Pigments, 1991, 17, 287-296,  Comparison of the INDO/S and the CNDO/S Method for the Absorption Wavelength Calculation of Organic Dyes. UdK      ( k    mKAcknowledgementsRThank you to George D. Purvis for providing some of the content for these slides .S8 S/:;NOPV [\^_`bdfhjlP  ` ̙33` ` ff3333f` 333MMM` f` f` 3>?" dZ@$z? " dZ@  @" `  n?" dZ(@   @@``PR    @ ` ` p>  >   K C  (  8 t<  <t    B-CDEF1))?,0, @t<    BYC1DEFt1))?+0-0X @t<m   B-CDEF1))?,0,, @<    BYC1DEFo 1))?X0-+0X0 @t ~  Ni @1?p  Z(xaxa1 ?H ( ? Slide Title  #   Tl(xaxa1 ?q ( ;Body Text Second Level Third Level Fourth Level Fifth Level     <   T(xaxa1?Y@ F*    Bd1?" R MDavid A. Gallagher 2004B  s *޽h ? qD=i( Default Design0 WOp( Ho{( #  T{lgg1 ? 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ZB hB s *8c?}ZB hB s *8c?{{ZB hB s *8c?00ZB hB s *8c?ZB hB s *8c?ZB hB s *8c?}UUZB hB s *8c?ZB hB s *8c?ZB hB s *8c?zzZB hB s *8c?..ZB hB s *8c?}ZB hB s *8c?ZB hB s *8c?TTZB hB s *8c?ZB hB s *8c?ZB hB s *8c?}yyZB h s *8c?i  @   i lB h <8c?V W >T v `  i#   fB hB 68c? ` l2 h <1?v  l2 h <1?H ` T  :  h# ) a `B hB 08c?: : 2N 9   h 9  f2 h 61?9 Q f2 h 61?y  T ]z   h#   `B hB 08c?]  2N z   h z  f2 h 61?z  f2 h 61?z  T  }  h# E~`B hB 08c? } 2N  Q  h  Q f2 h 61?  f2 h 61?9 Q T {   h#  `B hB 08c?  2N 1{   h 1{  f2 h 61?1{ I f2 h 61?q{  fB hB 68c?  fB hB 68c?fB hB 68c? h Z>lxaxa1?Z, <-6Z  h ZAlxaxa1?b <-7Z  h Z`Elxaxa1?jZ <-8Z  h ZhHlxaxa1?Rk <-9Z  h Z$Klxaxa1?g> N  =-10Z  h ZJlxaxa1?g NG  =-11Z  h Z4Rlxaxa1?g N  =-12Z  h ZtUlxaxa1?g N* =-13Z lB h <8c? J T  X  h#  k L `B hB 08c?X X 2N 1 5  h 1 5 f2 h 61?1 I5 f2 h 61?q 5 T  :  h#  N T `B hB 08c?: : 2N 9   h 9  f2 h 61?9 Q f2 i 61?y  T ]z   i#   `B iB 08c?]  2N z   i z  f2 i 61?z  f2 i 61?z  T  }  i# \ %`B iB 08c? } 2N  Q  i  Q f2  i 61?  f2  i 61?9 Q T {    i#  L`B  iB 08c?  2N 1{    i 1{  f2 i 61?1{ I f2 i 61?q{  fB iB 68c? LfB iB 68c? LfB iB 68c? L i 6^l1?> ,  *Transition instantly perturbs all orbitals++" i Hcl1?3  l4*Configuration Interaction (C. I.) improves accuracy55 H h 0޽h ? =Z{ s ___PPT10S + ڙD ' = @B D ' = @BA?%,( < +O%,( < +Dn' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*i%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<*iD' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<*iD{' =%(D#' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*i%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<*iD' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<*i+8+0+i0 +  ^ / ' P 4(  4 4 # lxaxa1 ?a<   j 4 BA1?@ (c j 4 BA1? `  4 Td 8c 8c8c?[g BGeometry W  4 T  8c 8c8c?x ` G SpectroscopicW 4 NH 8c 8c1?   MINDO/1 parameters YN  4 N4 8c 8c1?{ {5 zZerner s Intermediate Neglect of Differential Overlap (ZINDO) >Y>6  4 N 8c 8c1?Y |&Semiempirical quantum chemistry method 'Y'   4 N 8c 8c1? V   MINDO/S parameters Y<  4 H1?'t  4Ridley, Zerner , Theoret. Chim. Acta. 32, 111 (1973)55 PH 4 0޽h ? qD=i(V  .V&VU(    C x0? 8c 8c1 ?S   dB  <8c?J n h F     fB  68c?   Z0f 8c 8c8c?C"  j MO Energy eV a   T g6  # o^>   Zfxaxa1?g 6  ;-12Z   Z$dxaxa1?gS 6  ;-10Z   Z fxaxa1?2 :-8Z   ZAxaxa1?,= :-6Z   ZhExaxa1?z, :-4Z   ZHxaxa1?-2 :-2Z  Z0Lxaxa1?0d 90Z  Z0Oxaxa1?0 92ZT z  #  vN *   * ZB B s *8c? * ZB B s *8c?/ */ ZB B s *8c? * ZB B s *8c?*ZB B s *8c?B*BZB B s *8c?*ZB B s *8c?*ZB B s *8c?O*OZB B s *8c?*ZB B s *8c? * ZB B s *8c?i*iZB B s *8c?*ZB B s *8c?*ZB B s *8c?v*vZB  B s *8c?*ZB ! s *8c?%% `B "B 08c?|) ) `B #B 08c?|vv`B $B 08c?|  `B %B 08c?|/ / `B &B 08c?u  `B 'B 08c?|cc`B (B 08c?|`B )B 08c?|))`B *B 08c?|||2N EU + EUf2 , 61?EUf2 - 61?EU2N   .  f2 / 61? f2 0 61? 2N ~   1 ~  f2 2 61?~  f2 3 61?~  2N    4   f2 5 61?  f2 6 61?  2N    7   f2 8 61?  f2 9 61?  vN #(  : #( ZB ;B s *1? & ZB <B s *1?1 &1 ZB =B s *1? & ZB >B s *1?&ZB ?B s *1?>&>ZB @B s *1?&ZB AB s *1?&ZB BB s *1?K&KZB CB s *1?&ZB DB s *1? & ZB EB s *1?e&eZB FB s *1?&ZB GB s *1?&ZB HB s *1?r&rZB IB s *1?&ZB J s *1?(#( rB K BA,8c?2z1F > Tq L  k M c BACDE F31?P@@ ,X N c BACDE F31?P@@ ,XZB O s *1?ZB P s *1?+ZB Q s *1?wwZB R s *1?+ZB S s *1?ZB T s *1?+ZB U s *1?ZB V s *1?77+ZB W s *1?ZB X s *1?O O +ZB Y s *1?  ZB Z s *1?g g +ZB [ s *1?  ZB \ s *1?  +ZB ] s *1?  ZB ^ s *1?  +ZB _ s *1?  ZB ` s *1?  +ZB a s *1?77ZB b s *1?+ZB c s *1?OOZB d s *1?+ZB e s *1? ZB fB s *1?ZB gB s *1?ZB hB s *1?;;ZB iB s *1?  ZB jB s *1?s s ZB kB s *1?  ZB lB s *1?  ZB mB s *1?C C ZB nB s *1?   o Zgxaxa1?n.d ;200Z  p ZPkxaxa1?.| ;220Z  q Znxaxa1?. ;240Z  r Zrxaxa1?. ;260Z  s ZPuxaxa1?.  ;280Z  t Zxxaxa1? .  ;300Z  u Z|xaxa1? .  ;320Z  v Zxaxa1? .  ;340Z  w Zxaxa1?. .$ ;360Z  x Zpxaxa1?F.< ;380Z  y Zxaxa1?^.T ;400Z  z Z8xaxa1?NL 90Z  { Zpxaxa1?  =10000Z  | Zxaxa1?.   =20000Z  } Z8xaxa1?f   =30000Z  ~ ZȚxaxa1? ,  =40000Z   c zBCyDEF31?==xpppPp(h`XPH8h(H(h@`@ P0xX88hxXH8 0p8P800 pPX0@(  8XpxP({|@+ z  c JBCyDEF31?wwxpppp`pPp@p(hh``XXPPH@8x0h(X H8(hX@p(`P@0 hP@0 xhXH8((8Phxh0XHHh8( (08p8`8P8@800 ( p`pPX@P0@ 8((   08HXhpx`P@ @+   c ZBCDEdFl31?`@ `@ `@ 34@ :  c BCDEF31?//p`P@0 p`P@0 p`P@0 _`@   c B1C)DEF31?(0(( @    c B1C)DEF31?(0(( @    c B1C)DEF31?(0(( @k g   c B1C1DEF31?0000 @ 4   c B1C)DEF31?(0(( @c8  c B1C1DEF31?0000 @?Dp  ZHxaxa1?6 q JWavelength (nm)Z   Z<xaxa1? H)  ?MolarZ   Zxaxa1?>   ` Absorptivity Z     Zxaxa1?i   Bl/mol-cm Z  N S    S    c B)C)DEF31?(((( @S / | X   ZLxaxa1?V   ? PABAZ V  c .AH s-02* [ J  C "AI s-03 P^B  68c?>   H1?! `(*Location & structure aids design of dye)) H  0޽h ? =Zt  ^ ~vd(  d d 3 r0بxaxa1 ?   ( d 6d٨1?q dAbsorption intensity depends upon the overlap of the initial and final orbitals (transition dipole). exeG d 6Dި1?p0 W  GInitial orbital d 61?B  E Final orbitalV  d c .AH s-02O J  d C "AI s-03`V d c .AL s-06P `l s  ds ,$D0R  d C "AJ s-04sR  d C "AK s-05sJ fB dB 6Dp?  ^B d 6Dp? P ^B d 6Dp?" " XH d 0޽h ? qD=i(~___PPT10^+DB' = @B D' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*d%(+     HB (  H H # lh(xaxa1 ?H   5l ,P I H ,$D0r H BA1?,P (lB H <1?,,4  H H$1?`b I KZINDO approximationz    H   ,$D0x H HA1?  r H B1?<r H B1?m<p `B H 01?,`B H 01?tt`B  H 01?8y8`B  H 01?i4`B  HB 01? 8e 8`B  HB 01? ti t`B  HB 01? ` `B H 01?e e  H N81?&P  ARealityH H 0޽h ? qD=i(~___PPT10^++WDB' = @B D' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*H%(+&S ^ 0O(O N(    3 rȨxaxa1 ?HS   c$F     H  C 1 B % 3  BB & 3 1B BB ' 3 1B C BB ( 3 1  BB ) 3 12 3 BB * 3 1BB + 3 1"#BB , 3 1BB - 3 1B C BB . 3 1* Z BB / 3 1* Z BB 0 3 15* 6Z BB 1 3 1]* ^Z BB 2 3 1* Z BB 3 3 1* Z HB 4 C 8c: HB 5 C 8c U HB 6 C 8cU B HB 7 C 8cB Z HB 8 C 8cJ Z HB 9 C 8c" EJ HB : C 8cE }" HB ; C 8c}  HB < C 8c  HB = C 8cR 5 HB > C 8c5" mR HB ? C 8cm " HB @ C 8c  HB A C 8c % HB B C 8c% ] HB C C 8c]  HB D C 8c  HB E C 8cr  HB F C 8cj Mr HB G C 8cMb j HB H C 8cZ b HB I C 8cR Z HB J C 8cJ =R HB K C 8c=J }K HB L C 8c}B J HB M C 8cB C HB N C 8cB - C HB O C 8c- : m B HB P C 8cm : ; HB Q C 8c"HB R C 8cU:HB S C 8cU:HB T C 8cHB U C 8c HB V C 8c E*HB W C 8cE*}BHB X C 8c}BRHB Y C 8cRSHB Z C 8cR5SHB [ C 8c5JmRHB \ C 8cmBJHB ] C 8c:BHB ^ C 8c*%:HB _ C 8c%]*HB ` C 8c] HB a C 8c HB b C 8cHB c C 8cMHB d C 8cMHB e C 8cHB f C 8cHB g C 8c=HB h C 8c=}HB i C 8c}HB j C 8crHB k C 8cj- rHB l C 8c- Zm jHB m C 8cm R Z  < Pr  I-10*   <l `  H-5*   <U }b  G0*   <DUr} G5*   <mJ H10*   <dbm H15*   <H    I1.1*   <  )  I1.6*   <@ Q  I2.1*   <t   I2.6*   <TE   I3.1*   <u   I3.6* H  C 1 fB  61?fB  61?fB  61?fB  61?&N> N   BCDE$F,1? 5b@P%R~@M6  r  B1?NBr   B1?TJ   H"1?, p Qlow gradient* ~ narrow banddB  <D8c?D:'l Nh Nh,$D0,  Tt&xaxa1?N"h fHigher gradient allows access to more vibration levels from ground state and hence, higher band widthgg9$N  ;    ; H   C 1; ; B  3 ; ; BB  3 1  B BB  3 1{ B C BB  3 1{ BB  3 1{ 2 3 BB  3 1{  BB  3 1{ " #BB  3 1{  BB  3 1 B [C BB  3 1 * Z BB  3 1* Z BB  3 1* Z BB  3 1* Z BB  3 1C* DZ BB  3 1k* lZ HB  C 8c : HB  C 8c  HB  C 8c  CB HB  C 8cCB Z HB  C 8cJ Z HB  C 8c" J HB  C 8c 3" HB  C 8c3 s HB  C 8cs  HB  C 8cR  HB  C 8c" #R HB  C 8c# c" HB  C 8cc  HB  C 8c  HB  C 8c  HB  C 8c S HB  C 8cS  HB  C 8cr  HB  C 8cj r HB  C 8cb Cj HB  C 8cCZ {b HB  C 8c{R Z HB  C 8cJ R HB  C 8cJ 3K HB  C 8c3B kJ HB „ C 8ckB C HB Ä C 8cB C HB Ą C 8c: #B HB ń C 8c#: [; HB  C 8c C"HB  C 8cC"HB  C 8cZ HB  C 8cZ  HB  C 8c 3 HB  C 8c3 s" HB  C 8cs " HB  C 8c  HB  C 8c # HB  C 8c# c HB  C 8ccz  HB  C 8cR z HB  C 8c* R HB  C 8c S* HB  C 8cS HB  C 8cHB  C 8cHB  C 8cCHB  C 8cC{HB  C 8c{jHB  C 8cZjHB  C 8cR3ZHB  C 8c3BkRHB  C 8ck:BHB  C 8c2:HB  C 8c*#2HB  C 8c#"[*  <8   r  I-10*   <P=   H-5*   <4A  3 b  G0*   <LE r3  G5*   <H # J H10*   <L b#  H15*   <PK   I1.1*   <T{   I1.6*   <(Y   I2.1*    <] 7  I2.6*    <a _  I3.1*    <xe+   I3.6* H   C 1? 7 r  Ba1? M     BCDE$F,1? 5b@P%R~@6 R r   B1?M fB   61? | fB  61?" " fB  61?fB  61?rR&RfB  61?uI  Hj1? j Uhigh gradient* ~ broad bandlB  <D8c?  `B  01? x6 XB  01?1Z H  0޽h ? qD=i(~___PPT10^+lW*DB' = @B D' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*%(+| ^   L( ? L L # lxaxa1 ?HS   8 rr  L  x L HA1?rr rB L B1?> fB L 61?fl fB L 61?XD 0   L N@xaxa1?0N   fHigher gradient allows access to more vibration levels from ground state and hence, higher band width  ggR L H 1?XH Gradient calculated from the  excited state energy of the ground state geometryQQH L 0޽h ? qD=i(=   .;P(    3 r؀xaxa1 ?HS   f8 n<k +<nk@ | "a  kZB   s *Dp?Z"ZB   s *D8c?TZB   s *D8c?Z, ", ZB  s *D8c?TT T ZB  s *D8c?N| |   H1?AIa JS0, N | "a  n<! ZB  s *Dp?Z"ZB  s *D8c?TZB  s *D8c?Z, ", ZB  s *D8c?TT T ZB  s *D8c?N| |   H<1?AIa JS1, dB  <DԔ?  dB  <D1? dB  <D1?..  4 H1? Mground state geometry l Ej ;Ej,$D0T  0; -#  E@fB  6Dp?  fB  6D8c?   fB   6D8c? * * fB ! 6D8c? R R fB " 6D8c? z z  # T@1?"`? ; JS0, fB % 6Dp?  fB & 6D8c? fB ' 6D8c? fB ( 6D8c? fB ) 6D8c? 00 * TȨ1?"`)5  JS1, S  T$xaxa1? E %vibrational relaxation k > 1012 sec-1l&x ~B 1 NDp? ~B 2 NDp?$ ~B 3 NDp?p 0  5 H$1? Dj Pexcited singlet geometry: 6 H1?  x ,UV-visible Absorpton Spectrum k = 1015 sec-1X-$ l    9  ,$D0lB .B <DԔ?  lB / <D1?r r lB 0 <D1?2 2*  7 HP1?  #Fluorescence Spectrum k < 109 sec-1X$H  0޽h ? qD=i(___PPT10+7D~' = @B D9' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*;%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*9%(+ ^   9 (    3 rTxaxa1 ?Hi   B ) Hк1?  0UV-visible* max ~ 500nmZ '/   , . NL׺1?  .Fluorescence*  ~ 535nm@ d / C <A$fluorescein(EtOH)4Z l 0 C DA,fluorescein-S1-(EtOH)  l %2 < 92 %<,$D0t 8 68c?"`82 <@ %: & 5%8 &n 1 c >Afluorescence: & 2 <1?%h V g-Calculated Absorption & Fluorescence Spectra..z 3 C RA:fluorescein-dibase-structure# N 4 H\1?  Y fluorescein2-0  7 <1?~ D*H. Du, R. A. Fuh, J. Li, A. Corkan, J. S. Lindsey, "PhotochemCAD: A computer-aided design and research tool in photochemistry," Photochemistry and Photobiology, 68, 141-142, 1998  P  tH  0޽h ? qD=i(~___PPT10^+IDB' = @B D' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*9%(+   0b(  P 0 C (Afluor-23  / Hκ1?"`; =,$D0 6Fluorescence Emission Property of:  excited states Property:  optimized geometry Using:  PM3/CI........geometry Property of:  chemical sample Property:  UV-visible transitions Using:  current geometry ` x @`  3 rLxaxa1 ?HS     ) H1?"`;J  UV-visible Absorption Property of:  chemical sample Property:  UV-visible transitions Using:  ZINDO CI at PM3 geo... ` b x c @`H  0޽h ? qD=i(___PPT10+1ydDO' = @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*/%(+8+0+/0 +z ^  p(  p p # lp"xaxa1 ?TF$    p # l,#xaxa1 ? P 1    p T$xaxa8c?)F S  kQuestions answered:Z444OOiiZ8    p @   p  p S B CDEF1?  @  p c BC DEF)? @  p N18c8c8c?{ U nCalibrate before use W"444OOiiH p 0޽h ? qD=i(y___PPT10Y+D=' = @B +,  W,O, OT`+( ӱ ( xt ` ` # l?xaxa1 ?0r   [ P` Zl}xaxa1 ?dD -UV/Vis Absorption Maxima for CH3-(CH=CH)n-CHOl.Zx)F S  T` S  ` ZLxaxa1?5 9.T  t8  `#  8  ` Txxaxa1? t8  ;500  ` TQxaxa1?> (8  ;400  ` TTxaxa1? 8  ;300  ` TWxaxa1? 8  ;200 lT    `# s a ZB  ` s *1?  ZB  ` s *1?  ZB  ` s *1?`  ` ZB  ` s *1?  ZB  ` s *1?  ZB ` s *1?W W ZB ` s *1?  ZB ` s *1?  T    `# i  ` T\xaxa1?J   ;200  ` T_xaxa1? @  ;300  ` Tcxaxa1?  ;400  ` Tfxaxa1?  ;500 lT   `# Gs ZB `B s *1?  ZB `B s *1?7 7 ZB `B s *1?  ZB `B s *1?ZB `B s *1?WWZB `B s *1?ZB `B s *1?ZB ` s *1? l  ` <1?sY  T   #`#  ; Z !` s *1? ZB "` s *1?  T   &`# M i Z $` s *1? ZB %` s *1?  T    )`# a | Z '` s *1?  ZB (` s *1?   T   ' ,`# 6 R 'Z *` s *1?  'ZB +` s *1?   T  w  /`#  w Z -` s *1? w ZB .` s *1?   T   2`# d  Z 0` s *1? ZB 1` s *1? T   5`# , ZB 3`B s *1? ZB 4`B s *1?  6` s B%C!DEF1?$  @   7` s B%C!DEF1?$  @   8` s B%C!DEF1?$  @   9` s B$C!DEF1?#  @  , :` s B$C!DEF1?#  @h s  ;` s B%C!DEF1?$  @  ,T ~,  >`#  `B <`B 01?~, `B =`B 01?~, T    F`#    @      A`    Z ?` s *1?    ZB @` s *1?     B` Tqxaxa1?W s  Jat INDO/1 geometry  C` S B$C!DEF1?#  @ k !  D` Tuxaxa1?W C   Mat MOPAC AM1 geometry f E` 61?   G` Zyxaxa1?   Z"Calculated absorption maximum (nm)##x H` HA