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1
OUR CORPORATE SPONSORS
2006 Elsevier Publishing Award Gaussian,
Inc. Schrodinger, Inc. SemiChem Proctor and
Gamble Company ACS COMP Division
2
A Comparison of Ground and Excited State
Properties Using SCC-DFTB and Semiempirical
MethodsApplication to Dye Modeling

• Major Collaborators who wrote/provided most of
  the code
• TD-HF Code
• Sergei Tretiak
• TD-DFTB Code
• Thomas Niehaus
• Marsus Elstner
• Thomas Frauenheim

3
A B
C D
Lmax 626 525
382 435
E
F G
617
526 572
4
INDO/S CIS 10u/10d Errors Relative to
Experiment As Function of Geometry GEOMETRY A
M1 PM3 MMX Intercept 102.00 175.0 186.00
Slope 0.96 0.750 0.72 S.
D. 66.00 83.900 80.70 R2 0.53 0.250 0.30
Is the problem INDO/S or Geometry?
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INDO/S CIS 10u/10d ERRORS X-RAY
Geometry Intercept 21.10 Slope 1.15 S.
D. 27.50 R2 0.92 Solid stategeometry,
Solution spectra, Gas phase calculation !!!
6
INDO/S 10u/10d ERRORS Relative to Experiment As
Function of Geometry
________6-31G ________ GEOM X-RAY
B3LYP BLYP HF
HF/3-21G Intercept 21.10 63.00 14.00 -1.00 61
.00 Slope 1.15 1.07 1.18 1.31 1.14 S.
D. 27.50 43.90 37.60 62.40 56.00 R2 0.92 0.79 0
.85 0.58 0.66

Relative to X-RAY Geometry
___________6-31G_______
GEOMETRY B3LYP BLYP
HF HF/3-21G Intercept 23.50 -14.00 -55
.00 3.60 Slope 0.96 1.04 1.23 1.07 S.
D. 19.80 15.20 37.30 27.30 R2 0.94 0.97 0.79
0.89
7
INDO/S 10u/10d ERRORS Relative to Experiment As
Function of Geometry
________6-31G ______ GEOM X-RAY
B3LYP BLYP HF HF/3-21G DFTB Intercept
21.10 63.00 14.00 -1.00 61.00 -4.8 Slope 1.15
1.07 1.18 1.31 1.14 1.22 S. D. 27.50 43.90 37.6
0 62.40 56.00 39.33 R2 0.92 0.79 0.85 0.58 0.66
0.87

Relative to X-RAY Geometry
___________6-31G_______
GEOM B3LYP BLYP
HF HF/3-21G DFTB Intercept 23.5
0 -14.00 -55.00 3.60 -29.2
Slope 0.96 1.04 1.23 1.07 1.07 S.
D. 19.80 15.20 37.30 27.30 19.6 R2 0.94 0.97 0
.79 0.89 0.95 Geometry for largest dye
B3LYP/6-31G IBM 390 1 cpu-month G94
(1995)
DFTB
2.4 XEON 32 seconds
(2006)
8
A B
C D
Lmax 626 525
382 435
E
F G
617
526 572
9
Linear Acene Spectra n1,2,...10
Exp D. Bierman and W. Schmidt, JACS
109, 3163 (1980) n1,...6 PPP-CIS K. Hiruta,
S. Tokita, Y. Daikoku, and K. Nishimoto, J Photo.
Sci. Eng. 9, 73 (1996) TDDFT S. Grimme and M.
Parac, ChemPhysChem, 292 (2003) others
E. Kadantsev, M. Stott, and A. Rubio, J.
Chem. Phys. 124, 134901 (2006)
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Acene La Transition
N-M New? ao ao0.33/(? lumo - ? homo)
0.47 benzene-hexacene
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ACENE La INDO/S
13
Collective Effective Oscillator Method
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DYE Lmax INDO-S//B3LYP
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1Lb
1La
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Benzene Excited States
EXP. TD-DFTB Osc. Str. MOs
TD-PPP//B3LYP TD-INDOS//DFTB or B3LYP
262 nm 233 0. pgt p
253 (0.0)
266 (0.0) 208 218
0. p gt p 192 (0.0)
250 (0.0) -
193 0. s -gt p
-
- - 193 0.
s -gt p -
- -
193 0. s -gt p
-
- - 193
0. s -gt p -
- 187
183 0.44 pgt p
189 (0.87)
214 (0.56) 187 183 0.44
pgt p 189 (0.87)
214 (0.56)
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Tetracene Ground State Bond Lengths
BOND B3LYP DFTB AM1 NDDO-G GS GS GS GS a 1.45
3 1.445 1.430 1.442 b 1.412 1.415 1.413 1.413 c
1.394 1.401 1.387 1.398 d 1.435 1.435 1.438 1.43
2 e 1.368 1.373 1.361 1.373 f 1.432 1.426 1.431
1.419 g 1.453 1.443 1.437 1.444
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Tetracene Excited 1La Bond Lengths
BOND B3LYP DFTB AM1 NDDO-G 1La 1La 1La 1La a
1.450 1.445 1.455 1.451 b 1.402 1.412 1.400 1.40
7 c 1.413 1.418 1.411 1.419 d 1.408 1.416 1.414
1.413 e 1.393 1.398 1.383 1.393 f 1.396 1.401 1.
407 1.400 g 1.441 1.439 1.434 1.440 _____________
____________________ Dierksen and Grimme JCP
120, 3544 (2004)
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Tetracene 1Lb Bond Lengths
BOND AM1 DFTB NDDO-G 1Lb 1Lb 1Lb a 1.473 1.471
1.468 b 1.412 1.412 1.408 c 1.402 1.411 1.407 d
1.420 1.422 1.422 e 1.374 1.383 1.381 f 1.418 1.42
9 1.416 g 1.448 1.471 1.457
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Azulene
Symmetry Unconstrained Ground State (C2v)
RPA Symmetry Unconstrained
Excited States (C2v) 1A1
1B2 A1
_________________________________
__________________________________________
_________________________ ED
B3LYP DFTB NDDO-G EXP CASSCF
B3LYP DFTB NDDO-G CASSCF DFTB
NDDOG r1 1.399 1.401
1.405 1.402 1.395 1.401 1.395
1.400 1.400 1.419 1.413
1.403 r2 1.418 1.403
1.411 1.417 1.433 1.461 1.459
1.458 1.445 1.450 1.434
1.442 r3 1.383 1.388
1.397 1.394 1.441 1.441 1.433
1.444 1.412 1.447 1.416
1.388 r4 1.406 1.394
1.398 1.392 1.362 1.383 1.377
1.378 1.387 1.413 1.411
1.407 r5 1.403 1.394
1.399 1.393 1.409 1.419 1.410
1.417 1.400 1.409 1.407
1.394 rc 1.501 1.498
1.484 1.478 1.394 1.388 1.389
1.393 1.426 1.401 1.407
1.460 ________________________ Murakami, et.
al., J Chem Phys 120, 1245(2004) Dierksen and
Grimme, J Chem Pys 120, 3544 (2004)
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DFTB Ground and Excited State Geometries
S0 S1 a b 1.386
1.382 c 1.408 1.411 d 1.392 1.446 e
1.409 1.414 f 1.475 1.461 t 26
23
S0 a 1.204 b 1.476 c
1.402 d 1.392 e 1.408 f 1.476
t 30
S1 a 1.243 b 1.364 c 1.435 d
1.372 e 1.437 f 1.441 t 7
S0 S1 a 1.397 1.415 b
1.394 1.380 c 1.407 1.448 d 1.476
1.432 t 29 0.0
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DFTB Ground and Excited State Geometries
S0 S1 a 1.205 1.262 b 1.475
1.349 c 1..402 1.447 d 1.395 1.377 e
1.398 1.415 f g 1.398 1.406 h 1.394
1.447 i 1.409 1.416 j 1.385 1.384
S0 S1 S2 a 1.208
1.270 1.262 b 1.462 1.339 1.366 c
1.406 1.452 1.448 d 1.389 1.374
1.378 e 1.414 1.426 1.423 f 1.372
1.387 1.385
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DFTBGS Lmax 367nm(S2) DFTBS1 Lmax
430nm(S2) 63nm DFTBS2 Lmax 420nm(S2)
53nm
O
Stokes70nm
33
Acknowledgements

• Michael Zerner
• Filipp Furche
• Stefan Grimme
• Notke Rosch
• Alexander Voityuk
• ________________
• Deceased

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INDO/SPPP RPA PPP-CIS INDO/SPPP Ltd-CIS
36

Lmax INDO-S//B3LYP
37
2-Electron Integral (I-A) for R 0
MNDO/AM1/PM3 x 2 INDO/S x 1 NDDO-G ? MNDO
with INDO/S 2-center-2e integrals parameters
for geometry and UV-VIS for planar systems
38
DFTB Ground and Excited State Geometries
S0 a 1.208 b 1.462 c 1.406 d
1.389 e 1.414 f 1.372
S0 S1 S2 a 1.207 1.251
1.253 b 1.467 1.406 1.374 c 1.403
1.427 1.434 d 1.391 1.387 1.382 e
1.411 1.410 1.419 f 1.471 1.492
1.479 g 1.410 1.414 1.412 h 1.390
1.384 1.392 i 1.411 1.427 1.414 k
1.378 1.352 1.374 t 25.6 90 !
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S1 S2 a 1.270 1.262 b
1.339 1.366 c 1.452 1.448 d 1.374
1.378 e 1.426 1.423 f 1.387 1.385
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Curcumin
Computed
Measured AM1/RPA/COSMO Abs. Fl.
? Abs. Fl. ? Cyclohexane 422
489 67 409 444 35 Methanol
468 608 140 428
546 118 _________________________________
Bull. Korean Chem. Soc. 21, 81 (2000)