Jie Fu,1
Lazaro A. Padilha,1
David J. Hagan,1
Eric W. Van Stryland,1
Olga V. Przhonska,2
Mikhail V. Bondar,2
Yuriy L. Slominsky,3
and Alexei D. Kachkovski3
1College of Optics and Photonics: CREOL & FPCE; University of Central Florida, Orlando, FL 32816, USA, and Department of Physics, University of Central Florida, Orlando, FL 32816, USA
2Institute of Physics, National Academy of Sciences, Prospect Nauki 46, Kiev, 03028, Ukraine
3Institute of Organic Chemistry, National Academy of Sciences, Murmanskaya 5, Kiev, 03094, Ukraine
Jie Fu, Lazaro A. Padilha, David J. Hagan, Eric W. Van Stryland, Olga V. Przhonska, Mikhail V. Bondar, Yuriy L. Slominsky, and Alexei D. Kachkovski, "Molecular structure—two-photon absorption property relations in polymethine dyes," J. Opt. Soc. Am. B 24, 56-66 (2007)
We performed a comprehensive experimental investigation of two-photon absorption (2PA) spectra of a series of 12 symmetrical and asymmetrical cationic polymethine dyes, including complete one-and two-photon excitation anisotropy measurements. Quantum-chemical calculations were performed with the goal of understanding the nature of 2PA bands and of uncovering structure-property relations. We found that there are 2PA bands in the spectral region between the first absorption band and that for twice its energy. A weakly allowed 2PA band within the short-wavelength shoulder of the first absorption band was observed owing to the effects of vibrational and charge distribution symmetry breaking. The nature of the strongest 2PA band is connected to the electron transition from the molecular orbital localized at the benzene rings of the terminal groups to the lowest unoccupied molecular orbital (LUMO). Structure-property relations revealed that the 2PA cross section tends to be enhanced by either an increase in the length of the polymethine chromophore or an increase in the donor strengths in the terminal groups.
Jie Fu, Lazaro A. Padilha, David J. Hagan, Eric W. Van Stryland, Olga V. Przhonska, Mikhail V. Bondar, Yuriy L. Slominsky, and Alexei D. Kachkovski J. Opt. Soc. Am. B 24(1) 67-76 (2007)
Richard S. Lepkowicz, Claudiu M. Cirloganu, Jie Fu, Olga V. Przhonska, David J. Hagan, Eric W. Van Stryland, Mikhail V. Bondar, Yuriy L. Slominsky, and Alexei D. Kachkovski J. Opt. Soc. Am. B 22(12) 2664-2685 (2005)
Olga V. Przhonska, Jin Hong Lim, David J. Hagan, Eric W. Van Stryland, Mikhail V. Bondar, and Yurij L. Slominsky J. Opt. Soc. Am. B 15(2) 802-809 (1998)
Trenton R. Ensley, Honghua Hu, Matthew Reichert, Manuel R. Ferdinandus, Davorin Peceli, Joel M. Hales, Joseph W. Perry, Zhong’an Li, Sei-Hum Jang, Alex K.-Y. Jen, Seth R. Marder, David J. Hagan, and Eric W. Van Stryland J. Opt. Soc. Am. B 33(4) 780-796 (2016)
Meghana Rawal, Kerry E. Garrett, Lewis E. Johnson, Werner Kaminsky, Evgheni Jucov, David P. Shelton, Tatiana Timofeeva, Bruce E. Eichinger, Andreas F. Tillack, Bruce H. Robinson, Delwin L. Elder, and Larry R. Dalton J. Opt. Soc. Am. B 33(12) E160-E170 (2016)
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Measured and Calculated Parameters for PDs 25, 2646, and 2501 with Different Conjugation Lengthsa
Parameter
PD
25
2646
2501
(nm)
560
654
760
(D)
10.5
14
16.8
(D)
10.7
12.4
13.4
(nm) First band
515
585
655
(GM) First band
50
100
200
(nm) Second band
332
385
440
(GM) Second band
280
600
630
(D)
2.05
1.5
1.0
(D)
1.5
1.4
1.6
Detuning energy (eV)
0.36
0.29
0.32
n, number of repeated units in the chain; and , wavelength of the maxima of the one-photon absorption (1PA) and two-photon absorption (2PA). For comparison with linear absorption are presented as a function of , where is the excitation wavelength; and , ground-state transition dipole moments from experimental data and quantum-chemical calculations; , 2PA cross section (experimental uncertainties ); and , excited-state transition dipole moments from fitting based on Eq. (2) and quantum-chemical calculations.
Table 2
Measured and Calculated Parameters as Defined in Table 1 for PDs AF, 2350, 3428, and 824 with Different Conjugation Lengths
Parameter
PD
AF
2350
3428
824
(nm)
547
650
756
862
(D)
12.2
14.7
16.8
16.8
(D)
10.2
12.4
13.8
12.4
(nm) First band
490
590
665
740
(GM) First band
10
140
180
600
(nm) Second band
355
390
453
520
(GM) Second band
470
720
2280
2550
(D)
2.8
2.0
2.75
2.9
(D)
3.4
3.9
2.3
2.3
Detuning energy (eV)
0.51
0.31
0.26
0.25
Table 3
Measured and Calculated Parameters as Defined in Table 1 for PDs 2646, 2350, and 2630 with Different Terminal Groupsa and Same Conjugation Chain Length
Parameter
PD
2646 (Thiazolium)
2350 (Indolium)
2630 (Benzoindolium)
(nm)
654
650
690
(D)
14
14.7
14.1
(D)
12.4
12.4
11.2
(nm) First band
585
590
630
(GM) First band
100
140
150
(nm) Second band
385
390
440
(GM) Second band
600
720
900
(D)
1.5
2.0
3.1
(D)
1.4
3.9
3.0
Detuning energy (eV)
0.29
0.31
0.38
Terminal groups are in parentheses.
Table 4
Measured and Calculated Parameters as Defined in Table 1 for Symmetric Molecules PDs 25 and 2350 and for Asymmetric Molecules Styry1̱1 and PD 2665
Parameter
PD
25
Styry1̱1
2350
2665
(nm)
560
527
650
643
(D)
10.5
11.6
14.7
14
(D)
10.7
10.7
12.4
12.6
(nm) First band
515
500
590
585
(GM) First band
50
100
140
200
(nm) Second band
332
335
390
400
(GM) Second band
280
250
720
1000
(D)
2.05
2.5
2.0
1.75
(D)
1.5
2.4
3.9
1.7
Detuning energy (eV)
0.36
0.31
0.37
Table 5
Measured and Calculated Parameters as Defined in Table 1 for Bridged Molecules PDs 200 and 2093 and for Unbridged Molecules PDs 2646 and 3428
Parameter
PD
200
2646
2093
3428
(nm)
648
654
770
756
(D)
10.8
14
15.9
16.8
(D)
11.8
12.4
12.9
13.8
(nm) First band
580
585
670
665
(GM) First band
55
100
60
180
(nm) Second band
390
385
460
453
(GM) Second band
700
600
1200
2280
(D)
2.2
1.5
2.45
2.75
(D)
1.1
1.4
1.3
2.3
Detuning energy (eV)
0.32
0.29
0.26
0.26
Table 6
Calculated Parameters for the Unsubstituted Polymethine Chain and One Typical Polymethine Dye PD 2350
Dye
Transition
λ (nm)
Oscillator Strength
Symmetry of Final State
Main Configuration
Unsubstituted chain
551
1.65
315
0.002
291
0.08
PD 2350
655
1.6
460
0.01
410
0.07
395
0.02
(local)
386
0.06
352
0.05
Tables (6)
Table 1
Measured and Calculated Parameters for PDs 25, 2646, and 2501 with Different Conjugation Lengthsa
Parameter
PD
25
2646
2501
(nm)
560
654
760
(D)
10.5
14
16.8
(D)
10.7
12.4
13.4
(nm) First band
515
585
655
(GM) First band
50
100
200
(nm) Second band
332
385
440
(GM) Second band
280
600
630
(D)
2.05
1.5
1.0
(D)
1.5
1.4
1.6
Detuning energy (eV)
0.36
0.29
0.32
n, number of repeated units in the chain; and , wavelength of the maxima of the one-photon absorption (1PA) and two-photon absorption (2PA). For comparison with linear absorption are presented as a function of , where is the excitation wavelength; and , ground-state transition dipole moments from experimental data and quantum-chemical calculations; , 2PA cross section (experimental uncertainties ); and , excited-state transition dipole moments from fitting based on Eq. (2) and quantum-chemical calculations.
Table 2
Measured and Calculated Parameters as Defined in Table 1 for PDs AF, 2350, 3428, and 824 with Different Conjugation Lengths
Parameter
PD
AF
2350
3428
824
(nm)
547
650
756
862
(D)
12.2
14.7
16.8
16.8
(D)
10.2
12.4
13.8
12.4
(nm) First band
490
590
665
740
(GM) First band
10
140
180
600
(nm) Second band
355
390
453
520
(GM) Second band
470
720
2280
2550
(D)
2.8
2.0
2.75
2.9
(D)
3.4
3.9
2.3
2.3
Detuning energy (eV)
0.51
0.31
0.26
0.25
Table 3
Measured and Calculated Parameters as Defined in Table 1 for PDs 2646, 2350, and 2630 with Different Terminal Groupsa and Same Conjugation Chain Length
Parameter
PD
2646 (Thiazolium)
2350 (Indolium)
2630 (Benzoindolium)
(nm)
654
650
690
(D)
14
14.7
14.1
(D)
12.4
12.4
11.2
(nm) First band
585
590
630
(GM) First band
100
140
150
(nm) Second band
385
390
440
(GM) Second band
600
720
900
(D)
1.5
2.0
3.1
(D)
1.4
3.9
3.0
Detuning energy (eV)
0.29
0.31
0.38
Terminal groups are in parentheses.
Table 4
Measured and Calculated Parameters as Defined in Table 1 for Symmetric Molecules PDs 25 and 2350 and for Asymmetric Molecules Styry1̱1 and PD 2665
Parameter
PD
25
Styry1̱1
2350
2665
(nm)
560
527
650
643
(D)
10.5
11.6
14.7
14
(D)
10.7
10.7
12.4
12.6
(nm) First band
515
500
590
585
(GM) First band
50
100
140
200
(nm) Second band
332
335
390
400
(GM) Second band
280
250
720
1000
(D)
2.05
2.5
2.0
1.75
(D)
1.5
2.4
3.9
1.7
Detuning energy (eV)
0.36
0.31
0.37
Table 5
Measured and Calculated Parameters as Defined in Table 1 for Bridged Molecules PDs 200 and 2093 and for Unbridged Molecules PDs 2646 and 3428
Parameter
PD
200
2646
2093
3428
(nm)
648
654
770
756
(D)
10.8
14
15.9
16.8
(D)
11.8
12.4
12.9
13.8
(nm) First band
580
585
670
665
(GM) First band
55
100
60
180
(nm) Second band
390
385
460
453
(GM) Second band
700
600
1200
2280
(D)
2.2
1.5
2.45
2.75
(D)
1.1
1.4
1.3
2.3
Detuning energy (eV)
0.32
0.29
0.26
0.26
Table 6
Calculated Parameters for the Unsubstituted Polymethine Chain and One Typical Polymethine Dye PD 2350